Patent Publication Number: US-2023147066-A1

Title: Organic electroluminescent materials and devices

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Applications No. 63/399,248, filed on Aug. 19, 2022, No. 63/392,385, filed on Jul. 26, 2022, No. 63/391,173, filed on Jul. 21, 2022, No. 63/346,370, filed on May 27, 2022, No. 63/254,822, filed on Oct. 12, 2021, the entire contents of which are all incorporated herein by reference. This application is also a continuation-in-part of U.S. patent application Ser. No. 17/743,561, filed on May 13, 2022, which claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 63/295,235, filed on Dec. 30, 2021. This application is also a continuation-in-part of U.S. patent application Ser. No. 17/745,939, filed on May 17, 2022. 
    
    
     FIELD 
     The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices. 
     BACKGROUND 
     Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. 
     OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. 
     One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art. 
     SUMMARY 
     Provided are novel Ir(III) and Pt(II) complexes with organic ligands, substituted with a trialkylsylylmethyl, trialkylsilylethyl, a trialkylgermylmethyl, or a trialkylgermylethyl group. Introduction of such a group in the complex can improve efficiency of the emitters and facilitate sublimation 
     In one aspect, the present disclosure provides a compound having a formula of M(L A ) p (L B ) q (L C ) r , where L A  has a structure of Formula I, 
     
       
         
         
             
             
         
       
     
     L B  is a bidentate ligand; and L C  has a structure of Formula II, 
     
       
         
         
             
             
         
       
     
     In Formula I and Formula II: 
     p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the allowed number of bidentate ligands coordinating to the metal M; 
     when one of p, q, or r is greater than one, the respective L A , L B , or L C  can be same or different; 
     each of moiety A and moiety B independently represents a monocyclic 5-membered or 6-membered carbocyclic or heterocyclic ring, or a polycyclic, fused-ring structure comprising 5-membered and/or 6-membered carbocyclic or heterocyclic rings; 
     K 3  and K 4  are each independently a direct bond, O, or S; 
     each R A  and R B  independently represents mono, up to a maximum allowed number of substitutions, or no substitutions; 
     each of Z 1  and Z 2  is independently C or N; 
     at least one of R A , R B , R C1 , R C2 , or R C3  comprises a structure of Formula III 
     
       
         
         
             
             
         
       
     
     wherein L is a bivalent organic linker; 
     Z is Si or Ge; 
     each of R A , R B , R C1 , R C2 , and R C3  is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, selenyl, germyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; 
     each of R 1 , R 2 , and R 3  is independently a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, germyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; 
     L A  can be joined to one or both of L B  and L C  to form a tetradentate or hexadentate ligand; and 
     any two of R 1 , R 2 , R 3 , R A , R B , R C1 , R C2 , and R C3  can be joined or fused to form a ring, with a proviso that if Z is Si, and L is an aryl or heteroaryl linker linked to a N-containing 6-membered aromatic ring, then L is partially or fully deuterated, or partially or fully fluorinated; and if Z is Si and L is a linear alkyl linker, and if one of ring A and ring B is benzene and the other is pyridine, then L is linked to the pyridine ring. 
     In another aspect, the present disclosure provides a formulation including a compound of formula M(L A ) p (L B ) q (L C ) r  as described herein. 
     In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound of formula M(L A ) p (L B ) q (L C ) r  as described herein. 
     In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising a compound of formula M(L A ) p (L B ) q (L C ) r  as described herein. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG.  1    shows an organic light emitting device. 
         FIG.  2    shows an inverted organic light emitting device that does not have a separate electron transport layer. 
     
    
    
     DETAILED DESCRIPTION 
     A. Terminology 
     Unless otherwise specified, the below terms used herein are defined as follows: 
     As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules. 
     As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between. 
     As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form. 
     A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand. 
     As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level. 
     As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions. 
     The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine. 
     The term “acyl” refers to a substituted carbonyl radical (C(O)—R s ). 
     The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—R s  or —C(O)—O—R s ) radical. 
     The term “ether” refers to an —OR s  radical. 
     The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SR s  radical. 
     The term “selenyl” refers to a —SeR s  radical. 
     The term “sulfinyl” refers to a —S(O)—R s  radical. 
     The term “sulfonyl” refers to a —SO 2 —R s  radical. 
     The term “phosphino” refers to a —P(R s ) 3  radical, wherein each R s  can be same or different. 
     The term “silyl” refers to a —Si(R s ) 3  radical, wherein each R s  can be same or different. 
     The term “germyl” refers to a —Ge(R s ) 3  radical, wherein each R s  can be same or different. 
     The term “boryl” refers to a —B(R s ) 2  radical or its Lewis adduct —B(R s ) 3  radical, wherein R s  can be same or different. 
     In each of the above, R s  can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred R s  is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof. 
     The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted. 
     The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted. 
     The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group may be optionally substituted. 
     The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted. 
     The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted. 
     The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted. 
     The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted. 
     The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted. 
     The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted. 
     Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest. 
     The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents. 
     In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof. 
     In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof. 
     In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof. 
     In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. 
     The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R 1  represents mono-substitution, then one R 1  must be other than H (i.e., a substitution). Similarly, when R 1  represents di-substitution, then two of R 1  must be other than H. Similarly, when R 1  represents zero or no substitution, R 1 , for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms. 
     As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium. 
     The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein. 
     As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al.,  Tetrahedron  2015, 71, 1425-30 and Atzrodt et al.,  Angew. Chem. Int. Ed . ( Reviews ) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively. 
     It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent. 
     In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system. 
     B. The Compounds of the Present Disclosure 
     In one aspect, the present disclosure provides a compound having a formula of M(L A ) p (L B ) q (L C ) r , where L A  has a structure of Formula I, 
     
       
         
         
             
             
         
       
     
     L B  is a bidentate ligand; and L C  has a structure of Formula II, 
     
       
         
         
             
             
         
       
     
     In Formula I and Formula II: 
     p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the allowed number of bidentate ligands coordinating to the metal M; 
     when one of p, q, or r is greater than one, the respective L A , L B , or L C  can be the same or different; 
     each of moiety A and moiety B independently represents a monocyclic 5-membered or 6-membered carbocyclic or heterocyclic ring, or a polycyclic, fused-ring structure comprising 5-membered and/or 6-membered carbocyclic or heterocyclic rings; 
     K 3  and K 4  are each independently a direct bond, O, or S; 
     each R A  and R B  independently represents mono, up to a maximum allowed number of substitutions, or no substitutions; 
     each of Z 1  and Z 2  is independently C or N; 
     at least one of R A , R B , R C1 , R C2 , or R C3  comprises a structure of Formula III 
     
       
         
         
             
             
         
       
     
     wherein L is a bivalent organic linker; 
     Z is Si or Ge; 
     each of R A , R B , R C1 , R C2 , and R C3  is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, selenyl, germyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; 
     each of R 1 , R 2 , and R 3  is independently a substituent selected from the group consisting of the General Substituents defined herein; 
     L A  can be joined to one or both of L B  and L C  to form a tetradentate or hexadentate ligand; and 
     any two of R 1 , R 2 , R 3 , R A , R B , R C1 , R C2 , and R C3  can be joined or fused to form a ring, with a proviso that if Z is Si, and L is an aryl or heteroaryl linker linked to a N-containing 6-membered aromatic ring, then L is partially or fully deuterated, or partially or fully fluorinated; and if Z is Si and L is a linear alkyl linker, and if one of ring A and ring B is benzene and the other is pyridine, then L is linked to the pyridine ring. 
     In some embodiments, if Z is Si, and L is an aryl or heteroaryl linker linked to a N-containing 6-membered aromatic ring, then the compound is partially or fully deuterated, or partially or fully fluorinated. In some embodiments, L is a linear alkyl group. In some embodiments, if Z is Si and R A  or R B  comprises a structure of Formula III, then the compound is partially or fully deuterated, or partially or fully fluorinated. In some embodiments, when L is a linear alkyl group, Z is Si, and R A  or R B  comprises a structure of Formula III, then the compound is partially or fully deuterated, or partially or fully fluorinated. 
     In some embodiments, the compound has a structure of formula of M(L A ) p (L B ) q (L C ) r  and comprises at least a structure of Formula III. In some embodiments, only L A  or L C  comprises a structure of Formula III. In some embodiments, only L A  comprises one or more structures of Formula III. In some embodiments, only L C  comprises one or more structures of Formula III. In some embodiments, each of L A  and L C  comprises a structure of Formula III, which may be the same or different. 
     In some embodiments, the formula of M(L A ) p (L B ) q (L C ) r  does not include 
     
       
         
         
             
             
         
       
     
     In some embodiments, the formula of M(L A ) p (L B ) q (L C ) r  does not include 
     
       
         
         
             
             
         
       
     
     In some embodiments, the formula of M(L A ) p (L B ) q (L C ) r  does not include 
     
       
         
         
             
             
         
       
     
     In some embodiments, the formula of M(L A ) p (L B ) q (L C ) r  does not include 
     
       
         
         
             
             
         
       
     
     In some embodiments, the formula of M(L A ) p (L B ) q (L C ) r  does not include 
     
       
         
         
             
             
         
       
     
     In some embodiments, no ring with an N═O in the backbone is coordinated to the metal M. 
     In some embodiments, L A  is not joined with L B  to form a tetradentate ligand. In some embodiments, L A  is joined with L B  to form a tetradentate ligand. 
     In some embodiments, the compound is asymmetric or asymmetric. In some embodiments, the compound is partially or fully deuterated. 
     In some embodiments, R A  is not joined with an R B  to form a ring. 
     In some embodiments, each of R A , R B , R C1 , R C2 , and R C3  is independently a hydrogen or a substituent selected from the group consisting of the Preferred General Substituents defined herein. In some embodiments, each of R A , R B , R C1 , R C2 , and R C3  is independently a hydrogen or a substituent selected from the group consisting of the More Preferred General Substituents defined herein. In some embodiments, each of R A , R B , R C1 , R C2 , and R C3  is independently a hydrogen or a substituent selected from the group consisting of the Most Preferred General Substituents defined herein. 
     In some embodiments, each of R 1 , R 2 , and R 3  is independently a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof. 
     In some embodiments, L is selected from the group consisting of alkyl, partially or fully fluorinated alkyl, partially or fully deuterated alkyl, cycloalkyl, partially or fully fluorinated cycloalkyl, partially or fully deuterated cycloalkyl, aryl, partially or fully fluorinated aryl, partially or fully deuterated aryl, heteroaryl, partially or fully fluorinated heteroaryl, partially or fully deuterated heteroaryl, and combinations thereof; and L can be further substituted. 
     In some embodiments, L forms a ring with at least one of R 1 , R 2 , or R 3 . In some embodiments, L does not form a ring with any one of R 1 , R 2 , or R 3 . 
     In some embodiments, one of Z 1  and Z 2  is C and the other one of Z 1  and Z 2  is N. 
     In some embodiments, Z 1  is C and Ring A is a polycyclic, fused-ring structure. In some such embodiments, R A  comprises the structure of Formula III. 
     In some embodiments, Z 2  is C and Ring B is a polycyclic, fused-ring structure. In some such embodiments, R B  comprises the structure of Formula III. 
     In some embodiment, the polycyclic, fused-ring structure comprises at least 3 rings. In some embodiments, the polycyclic, fused-ring structure comprises at least 4 rings. 
     In some embodiments, Formula III has a structure of Formula IIIA, 
     
       
         
         
             
             
         
       
     
     In Formula IIIA, n is 1 or 2; each R 4  and R 5  is independently selected from the group consisting of H, D, F, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl; and at least one of R 4  and R 5  is not H. 
     In some embodiments of Formula IIIA, neither R 4  nor R 5  is H. In some embodiments of Formula IIIA, both R 4  and R 5  are H. In some embodiments of Formula IIIA, both R 4  and R 5  are D. In some embodiments of Formula IIIA, each of R 4  and R 5  is independently selected from the group consisting of D, F, and alkyl. 
     In some embodiments, L comprises an aromatic linker. 
     In some embodiments, M can be Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu. In some embodiments, M can be Ir or Pt. 
     In some embodiments, p is 1 or 2. In some embodiments, p is 3. 
     In some embodiments, q is 0. In some embodiments, q is 1 or 2. 
     In some embodiments, r is 0. In some embodiments, r is 1 or 2. 
     In some embodiments, the compound comprises at least two structures of Formula III or IIIA. In some embodiments, the compound comprises at least two structures of Formula III. In some embodiments, the compound comprises at least two structures of Formula IIIA. In some embodiments, each of the at least two structures of Formula III or IIIA is the same. In some embodiments, each of the at least two structures of Formula III or IIIA is different. 
     In some embodiments, the compound comprises at least three structures of Formula III or IIIA. In some embodiments, the compound comprises at least three structures of Formula III. In some embodiments, the compound comprises at least three structures of Formula IIIA. In some embodiments, each of the at least three structures of Formula III or IIIA is the same. In some embodiments, each of the at least three structures of Formula III or IIIA is different. In some embodiments, at least two of the structures of Formula III or IIIA are the same and at least one of the structures of Formula III or IIIA is different. 
     In some embodiments, the compound has a formula selected from the group consisting of Ir(L A ) 3 , Ir(L A ) 2 (L B ), and Ir(L A )(L B ) 2 , Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), and Ir(L A )(L B )(L C ), and for each formula only L A  comprises a structure of Formula III or Formula IIIA. 
     In some embodiments, the compound has a formula selected from the group consisting of Ir(L A ) 3 , Ir(L A ) 2 (L B ), and Ir(L A )(L B ) 2 , Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), and Ir(L A )(L B )(L C ), and for each formula at least L A  comprises a structure of Formula III or Formula IIIA. 
     In some embodiments, the compound has a formula selected from the group consisting of Ir(L A ) 2 (L B ), Ir(L A )(L B ) 2 , and Ir(L A )(L B )(L C ), and for each formula, ligand L A  comprises a structure of Formula III or Formula IIIA, and, when present, L B  also comprises a structure of Formula III or Formula IIIA, which may be the same or different from the structure of Formula III or Formula IIIA of ligand L A . In some such embodiments, the compound has a formula selected from the group consisting of Ir(L A ) 2 (L B ) and Ir(L A )(L B ) 2 . In some such embodiments of formula Ir(L A )(L B )(L C ), L C  also comprises a structure of Formula III or Formula IIIA, which may be the same or different from the structure of Formula III or Formula IIIA of ligand L A  or L B . In some such embodiments of formula Ir(L A )(L B )(L C ), L C  does not comprise a structure of Formula III or Formula IIIA. 
     In some embodiments, the compound has the formula selected from the group consisting of Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), and Ir(L A )(L B )(L C ), and for each formula ligand L A  comprises a structure of Formula III or Formula IIIA, and L C  also comprises at least one structure of Formula III or Formula IIIA. In some such embodiments of formula Ir(L A )(L B )(L C ), L B  also comprises a structure of Formula III or Formula IIIA. In some such embodiments of formula Ir(L A )(L B )(L C ), L B  does not comprise a structure of Formula III or Formula IIIA. 
     In some embodiments, the compound has the formula selected from the group consisting of Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), and Ir(L A )(L B )(L C ), and for each formula only L C  comprises one or more of a structure of Formula III or Formula IIIA. 
     In the embodiments having a formula selected from the group consisting of Ir(L A ) 3 , Ir(L A ) 2 (L B ), Ir(L A )(L B ) 2 , Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), and Ir(L A )(L B )(L C ), each of the structures of Formula III or Formula IIIA are structures of Formula III. 
     In the embodiments having a formula selected from the group consisting of Ir(L A ) 3 , Ir(L A ) 2 (L B ), Ir(L A )(L B ) 2 , Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), and Ir(L A )(L B )(L C ), each of the structures of Formula III or Formula IIIA are structures of Formula IIIA. 
     In the embodiments having a formula selected from the group consisting of Ir(L A ) 3 , Ir(L A ) 2 (L B ), Ir(L A )(L B ) 2 , Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), and Ir(L A )(L B )(L C ), at least one of the structures of Formula III or Formula IIIA is a structure of Formula III and at least one of the structures of Formula III or Formula IIIA is a structure of Formula IIIA. 
     In some embodiments, the compound has a formula of Pt(L A )(L B ); and wherein L A  and L B  can be same or different, and at least one of L A  or L B  comprises a structure of Formula III or Formula IIIA. In some embodiments, the compound has a formula of Pt(L A )(L B ); and wherein L A  and L B  can be same or different, and at least one of L A  or L B  comprises a structure of Formula III. In some embodiments, the compound has a formula of Pt(L A )(L B ); and wherein L A  and L B  can be same or different, and at least one of L A  or L B  comprises a structure of Formula IIIA. In some embodiments, both of L A  and L B  comprise at least one structure of Formula III or Formula IIIA, which may be the same or different. 
     In some embodiments, having a formula of Pt(L A )(L B ), L A  and L B  are connected to form a tetradentate ligand. 
     In some embodiments, the ligand L A  is selected from the group consisting of the structures of the following 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein: 
     X A  is C or N; and 
     Z A  is O, S, NR or Se; 
     R A1 , R A2  and R A3  represent mono- to maximum possible substitution or no substitution; 
     each R, R A1 , R A2 , and R A3  is independently a hydrogen or a substituent selected from the group consisting of the General Substituents defined herein, and 
     except for compounds of formula Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), or Ir(L A )(L B )(L C ), where only L C  comprises a structure of Formula III or Formula IIIA, at least one of R A1 , R A2  and R A3  comprises a structure of Formula III or Formula IIIA. 
     In some embodiments where L A  has a structure of LIST 1, the compound has a structure of formula Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), or Ir(L A )(L B )(L C ), and only L C  comprises a structure of Formula III or Formula IIIA. 
     In some embodiments where L A  has a structure of LIST 1, the compound has a structure of formula Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), or Ir(L A )(L B )(L C ), and at least one of L A  or L B  comprises at least one structure of Formula III or Formula IIIA. 
     In some embodiments where L A  has a structure of LIST 1, the compound does not have a structure of formula Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), or Ir(L A )(L B )(L C ), and L A  comprises at least one structure of Formula III or Formula IIIA. 
     In some embodiments, ligand L A  is selected from the group consisting of the structures of the following 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein: 
     each R A1 , R A2  and R A3  represents mono- to maximum possible substitution or no substitution; 
     each of R A1 , R A2 , R A3 , and R A4  is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, selenyl, germyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, 
     except for compounds of formula Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), or Ir(L A )(L B )(L C ), where only L C  comprises a structure of Formula III or Formula IIIA, at least one of R A1 , R A2  and R A3  comprises a structure of Formula III or Formula IIIA. 
     In some embodiments where L A  has a structure of LIST 2, the compound has a structure of formula Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), or Ir(L A )(L B )(L C ), and only L C  comprises a structure of Formula III or Formula IIIA. 
     In some embodiments where L A  has a structure of LIST 2, the compound has a structure of formula Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), or Ir(L A )(L B )(L C ), and at least one of L A  or L B  comprises at least one structure of Formula III or Formula IIIA. 
     In some embodiments where L A  has a structure of LIST 2, the compound does not have a structure of formula Ir(L A )(L C ) 2 , Ir(L A ) 2 (L C ), or Ir(L A )(L B )(L C ), and L A  comprises at least one structure of Formula III or Formula IIIA. 
     In some embodiments, the ligand L A  is selected from the group consisting of the structures of the following 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments where Ligand L A  does not comprise a structure of Formula III or Formula IIIA, and the ligand L A  is selected from the group consisting of the structures of the following LIST 4: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments, L B  comprises a structure of Formula III or Formula IIIA. In some embodiments, L B  comprises a structure of Formula III. In some embodiments, L B  comprises a structure of Formula IIIA. 
     In some embodiments, ligand L B  is selected from the group consisting of the structures of the following 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments, ligand L B  is a substituted or unsubstituted phenylpyridine. 
     In some embodiments, any ligand L B  is independently selected from the group consisting of the structures of the following LIST 6: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein T is selected from the group consisting of B, Al, Ga, and In;
 
wherein K 1′  is a direct bond or is selected from the group consisting of NR e , PR e , O, S, and Se;
 
wherein each Y 1  to Y 13  are independently selected from the group consisting of carbon and nitrogen;
 
wherein Y′ is selected from the group consisting of BR e , BR e R f , NR e , PR e , P(O)R e , O, S, Se, C═O, C═S, C═Se, C═NR e , C═CR e R f , S═O, SO 2 , CR e R f , SiR e R f , and GeR e R f ;
 
wherein R e  and R f  can be fused or joined to form a ring;
 
wherein each R a , R b , R c , and R d  can independently represent from mono to the maximum possible number of substitutions, or no substitution;
 
wherein each R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e , and R f  is independently a hydrogen or a substituent selected from the group consisting of the General Substituents as defined herein; and
 
wherein any two of R a1 , R b1 , R c1 , R d1 , R a , R b , R c , and R d  can be fused or joined to form a ring or form a multidentate ligand.
 
     In some embodiments, any L B  is independently selected from the group consisting of the structures of the following LIST 7: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein R a ′, R b ′, R c ′, R d ′, and R e ′ each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring;
 
wherein R a ′, R b ′, R c ′, R d ′, and R e ′ each independently hydrogen or a substituent selected from the group consisting of the general substituents as defined herein; and
 
wherein two adjacent substituents of R a ′, R b ′, R c ′, R d ′, and R e ′ can be fused or joined to form a ring or form a multidentate ligand.
 
     In some embodiments, at least one L B  is present and is selected from L Bk , wherein k is an integer from 1 to 324; and L B1  to L B324  have structures defined in the following LIST 8: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments, ligand L C  is present and is selected from the group consisting of the structures of the following LIST 9: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments, ligand L C  is present and is selected from the group consisting of L Cj-I  and L Cj-II , wherein each L Cj-I  has a structure based on formula 
     
       
         
         
             
             
         
       
     
     and 
     each L Cj-II  has a structure based on formula 
     
       
         
         
             
             
         
       
     
     wherein for each L Cj  in L Cj-I  and L Cj-II , R 201  and R 202  are each independently defined in the following LIST 10: 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
               
               
             
               
                   
               
               
                 L Cj   
                 R 201   
                 R 202   
                 L Cj   
                 R 201   
                 R 202   
                 L Cj   
                 R 201   
                 R 202   
                 L Cj   
                 R 201   
                 R 202   
               
               
                   
               
             
            
               
                 L C1   
                 R D1   
                 R D1   
                 L C193   
                 R D1   
                 R D3   
                 L C385   
                 R D17   
                 R D40   
                 L C577   
                 R D143   
                 R D120   
               
               
                 L C2   
                 R D2   
                 R D2   
                 L C194   
                 R D1   
                 R D4   
                 L C386   
                 R D17   
                 R D41   
                 L C578   
                 R D143   
                 R D133   
               
               
                 L C3   
                 R D3   
                 R D3   
                 L C195   
                 R D1   
                 R D5   
                 L C387   
                 R D17   
                 R D42   
                 L C579   
                 R D143   
                 R D134   
               
               
                 L C4   
                 R D4   
                 R D4   
                 L C196   
                 R D1   
                 R D9   
                 L C388   
                 R D17   
                 R D43   
                 L C580   
                 R D143   
                 R D135   
               
               
                 L C5   
                 R D5   
                 R D5   
                 L C197   
                 R D1   
                 R D10   
                 L C389   
                 R D17   
                 R D48   
                 L C581   
                 R D143   
                 R D136   
               
               
                 L C6   
                 R D6   
                 R D6   
                 L C198   
                 R D1   
                 R D17   
                 L C390   
                 R D17   
                 R D49   
                 L C582   
                 R D143   
                 R D144   
               
               
                 L C7   
                 R D7   
                 R D7   
                 L C199   
                 R D1   
                 R D18   
                 L C391   
                 R D17   
                 R D50   
                 L C583   
                 R D143   
                 R D145   
               
               
                 L C8   
                 R D8   
                 R D8   
                 L C200   
                 R D1   
                 R D20   
                 L C392   
                 R D17   
                 R D54   
                 L C584   
                 R D143   
                 R D146   
               
               
                 L C9   
                 R D9   
                 R D9   
                 L C201   
                 R D1   
                 R D22   
                 L C393   
                 R D17   
                 R D55   
                 L C585   
                 R D143   
                 R D147   
               
               
                 L C10   
                 R D10   
                 R D10   
                 L C202   
                 R D1   
                 R D37   
                 L C394   
                 R D17   
                 R D58   
                 L C586   
                 R D143   
                 R D149   
               
               
                 L C11   
                 R D11   
                 R D11   
                 L C203   
                 R D1   
                 R D40   
                 L C395   
                 R D17   
                 R D59   
                 L C587   
                 R D143   
                 R D151   
               
               
                 L C12   
                 R D12   
                 R D12   
                 L C204   
                 R D1   
                 R D41   
                 L C396   
                 R D17   
                 R D78   
                 L C588   
                 R D143   
                 R D154   
               
               
                 L C13   
                 R D13   
                 R D13   
                 L C205   
                 R D1   
                 R D42   
                 L C397   
                 R D17   
                 R D79   
                 L C589   
                 R D143   
                 R D155   
               
               
                 L C14   
                 R D14   
                 R D14   
                 L C206   
                 R D1   
                 R D43   
                 L C398   
                 R D17   
                 R D81   
                 L C590   
                 R D143   
                 R D161   
               
               
                 L C15   
                 R D15   
                 R D15   
                 L C207   
                 R D1   
                 R D48   
                 L C399   
                 R D17   
                 R D87   
                 L C591   
                 R D143   
                 R D175   
               
               
                 L C16   
                 R D16   
                 R D16   
                 L C208   
                 R D1   
                 R D49   
                 L C400   
                 R D17   
                 R D88   
                 L C592   
                 R D144   
                 R D3   
               
               
                 L C17   
                 R D17   
                 R D17   
                 L C209   
                 R D1   
                 R D50   
                 L C401   
                 R D17   
                 R D89   
                 L C593   
                 R D144   
                 R D5   
               
               
                 L C18   
                 R D18   
                 R D18   
                 L C210   
                 R D1   
                 R D54   
                 L C402   
                 R D17   
                 R D93   
                 L C594   
                 R D144   
                 R D17   
               
               
                 L C19   
                 R D19   
                 R D19   
                 L C211   
                 R D1   
                 R D55   
                 L C403   
                 R D17   
                 R D116   
                 L C595   
                 R D144   
                 R D18   
               
               
                 L C20   
                 R D20   
                 R D20   
                 L C212   
                 R D1   
                 R D58   
                 L C404   
                 R D17   
                 R D117   
                 L C596   
                 R D144   
                 R D20   
               
               
                 L C21   
                 R D21   
                 R D21   
                 L C213   
                 R D1   
                 R D59   
                 L C405   
                 R D17   
                 R D118   
                 L C597   
                 R D144   
                 R D22   
               
               
                 L C22   
                 R D22   
                 R D22   
                 L C214   
                 R D1   
                 R D78   
                 L C406   
                 R D17   
                 R D119   
                 L C598   
                 R D144   
                 R D37   
               
               
                 L C23   
                 R D23   
                 R D23   
                 L C215   
                 R D1   
                 R D79   
                 L C407   
                 R D17   
                 R D120   
                 L C599   
                 R D144   
                 R D40   
               
               
                 L C24   
                 R D24   
                 R D24   
                 L C216   
                 R D1   
                 R D81   
                 L C408   
                 R D17   
                 R D133   
                 L C600   
                 R D144   
                 R D41   
               
               
                 L C25   
                 R D25   
                 R D25   
                 L C217   
                 R D1   
                 R D87   
                 L C409   
                 R D17   
                 R D134   
                 L C601   
                 R D144   
                 R D42   
               
               
                 L C26   
                 R D26   
                 R D26   
                 L C218   
                 R D1   
                 R D88   
                 L C410   
                 R D17   
                 R D135   
                 L C602   
                 R D144   
                 R D43   
               
               
                 L C27   
                 R D27   
                 R D27   
                 L C219   
                 R D1   
                 R D89   
                 L C411   
                 R D17   
                 R D136   
                 L C603   
                 R D144   
                 R D48   
               
               
                 L C28   
                 R D28   
                 R D28   
                 L C220   
                 R D1   
                 R D93   
                 L C412   
                 R D17   
                 R D143   
                 L C604   
                 R D144   
                 R D49   
               
               
                 L C29   
                 R D29   
                 R D29   
                 L C221   
                 R D1   
                 R D116   
                 L C413   
                 R D17   
                 R D144   
                 L C605   
                 R D144   
                 R D54   
               
               
                 L C30   
                 R D30   
                 R D30   
                 L C222   
                 R D1   
                 R D117   
                 L C414   
                 R D17   
                 R D145   
                 L C606   
                 R D144   
                 R D58   
               
               
                 L C31   
                 R D31   
                 R D31   
                 L C223   
                 R D1   
                 R D118   
                 L C415   
                 R D17   
                 R D146   
                 L C607   
                 R D144   
                 R D59   
               
               
                 L C32   
                 R D32   
                 R D32   
                 L C224   
                 R D1   
                 R D119   
                 L C416   
                 R D17   
                 R D147   
                 L C608   
                 R D144   
                 R D78   
               
               
                 L C33   
                 R D33   
                 R D33   
                 L C225   
                 R D1   
                 R D120   
                 L C417   
                 R D17   
                 R D149   
                 L C609   
                 R D144   
                 R D79   
               
               
                 L C34   
                 R D34   
                 R D34   
                 L C226   
                 R D1   
                 R D133   
                 L C418   
                 R D17   
                 R D151   
                 L C610   
                 R D144   
                 R D81   
               
               
                 L C35   
                 R D35   
                 R D35   
                 L C227   
                 R D1   
                 R D134   
                 L C419   
                 R D17   
                 R D154   
                 L C611   
                 R D144   
                 R D87   
               
               
                 L C36   
                 R D36   
                 R D36   
                 L C228   
                 R D1   
                 R D135   
                 L C420   
                 R D17   
                 R D155   
                 L C612   
                 R D144   
                 R D88   
               
               
                 L C37   
                 R D37   
                 R D37   
                 L C229   
                 R D1   
                 R D136   
                 L C421   
                 R D17   
                 R D161   
                 L C613   
                 R D144   
                 R D89   
               
               
                 L C38   
                 R D38   
                 R D38   
                 L C230   
                 R D1   
                 R D143   
                 L C422   
                 R D17   
                 R D175   
                 L C614   
                 R D144   
                 R D93   
               
               
                 L C39   
                 R D39   
                 R D39   
                 L C231   
                 R D1   
                 R D144   
                 L C423   
                 R D50   
                 R D3   
                 L C615   
                 R D144   
                 R D116   
               
               
                 L C40   
                 R D40   
                 R D40   
                 L C232   
                 R D1   
                 R D145   
                 L C424   
                 R D50   
                 R D5   
                 L C616   
                 R D144   
                 R D117   
               
               
                 L C41   
                 R D41   
                 R D41   
                 L C233   
                 R D1   
                 R D146   
                 L C425   
                 R D50   
                 R D18   
                 L C617   
                 R D144   
                 R D118   
               
               
                 L C42   
                 R D42   
                 R D42   
                 L C234   
                 R D1   
                 R D147   
                 L C426   
                 R D50   
                 R D20   
                 L C618   
                 R D144   
                 R D119   
               
               
                 L C43   
                 R D43   
                 R D43   
                 L C235   
                 R D1   
                 R D149   
                 L C427   
                 R D50   
                 R D22   
                 L C619   
                 R D144   
                 R D120   
               
               
                 L C44   
                 R D44   
                 R D44   
                 L C236   
                 R D1   
                 R D151   
                 L C428   
                 R D50   
                 R D37   
                 L C620   
                 R D144   
                 R D133   
               
               
                 L C45   
                 R D45   
                 R D45   
                 L C237   
                 R D1   
                 R D154   
                 L C429   
                 R D50   
                 R D40   
                 L C621   
                 R D144   
                 R D134   
               
               
                 L C46   
                 R D46   
                 R D46   
                 L C238   
                 R D1   
                 R D155   
                 L C430   
                 R D50   
                 R D41   
                 L C622   
                 R D144   
                 R D135   
               
               
                 L C47   
                 R D47   
                 R D47   
                 L C239   
                 R D1   
                 R D161   
                 L C431   
                 R D50   
                 R D42   
                 L C623   
                 R D144   
                 R D136   
               
               
                 L C48   
                 R D48   
                 R D48   
                 L C240   
                 R D1   
                 R D175   
                 L C432   
                 R D50   
                 R D43   
                 L C624   
                 R D144   
                 R D145   
               
               
                 L C49   
                 R D49   
                 R D49   
                 L C241   
                 R D4   
                 R D3   
                 L C433   
                 R D50   
                 R D48   
                 L C625   
                 R D144   
                 R D146   
               
               
                 L C50   
                 R D50   
                 R D50   
                 L C242   
                 R D4   
                 R D5   
                 L C434   
                 R D50   
                 R D49   
                 L C626   
                 R D144   
                 R D147   
               
               
                 L C51   
                 R D51   
                 R D51   
                 L C243   
                 R D4   
                 R D9   
                 L C435   
                 R D50   
                 R D54   
                 L C627   
                 R D144   
                 R D149   
               
               
                 L C52   
                 R D52   
                 R D52   
                 L C244   
                 R D4   
                 R D10   
                 L C436   
                 R D50   
                 R D55   
                 L C628   
                 R D144   
                 R D151   
               
               
                 L C53   
                 R D53   
                 R D53   
                 L C245   
                 R D4   
                 R D17   
                 L C437   
                 R D50   
                 R D58   
                 L C629   
                 R D144   
                 R D154   
               
               
                 L C54   
                 R D54   
                 R D54   
                 L C246   
                 R D4   
                 R D18   
                 L C438   
                 R D50   
                 R D59   
                 L C630   
                 R D144   
                 R D155   
               
               
                 L C55   
                 R D55   
                 R D55   
                 L C247   
                 R D4   
                 R D20   
                 L C439   
                 R D50   
                 R D78   
                 L C631   
                 R D144   
                 R D161   
               
               
                 L C56   
                 R D56   
                 R D56   
                 L C248   
                 R D4   
                 R D22   
                 L C440   
                 R D50   
                 R D79   
                 L C632   
                 R D144   
                 R D175   
               
               
                 L C57   
                 R D57   
                 R D57   
                 L C249   
                 R D4   
                 R D37   
                 L C441   
                 R D50   
                 R D81   
                 L C633   
                 R D145   
                 R D3   
               
               
                 L C58   
                 R D58   
                 R D58   
                 L C250   
                 R D4   
                 R D40   
                 L C442   
                 R D50   
                 R D87   
                 L C634   
                 R D145   
                 R D5   
               
               
                 L C59   
                 R D59   
                 R D59   
                 L C251   
                 R D4   
                 R D41   
                 L C443   
                 R D50   
                 R D88   
                 L C635   
                 R D145   
                 R D17   
               
               
                 L C60   
                 R D60   
                 R D60   
                 L C252   
                 R D4   
                 R D42   
                 L C444   
                 R D50   
                 R D89   
                 L C636   
                 R D145   
                 R D18   
               
               
                 L C61   
                 R D61   
                 R D61   
                 L C253   
                 R D4   
                 R D43   
                 L C445   
                 R D50   
                 R D93   
                 L C637   
                 R D145   
                 R D20   
               
               
                 L C62   
                 R D62   
                 R D62   
                 L C254   
                 R D4   
                 R D48   
                 L C446   
                 R D50   
                 R D116   
                 L C638   
                 R D145   
                 R D22   
               
               
                 L C63   
                 R D63   
                 R D63   
                 L C255   
                 R D4   
                 R D49   
                 L C447   
                 R D50   
                 R D117   
                 L C639   
                 R D145   
                 R D37   
               
               
                 L C64   
                 R D64   
                 R D64   
                 L C256   
                 R D4   
                 R D50   
                 L C448   
                 R D50   
                 R D118   
                 L C640   
                 R D145   
                 R D40   
               
               
                 L C65   
                 R D65   
                 R D65   
                 L C257   
                 R D4   
                 R D54   
                 L C449   
                 R D50   
                 R D119   
                 L C641   
                 R D145   
                 R D41   
               
               
                 L C66   
                 R D66   
                 R D66   
                 L C258   
                 R D4   
                 R D55   
                 L C450   
                 R D50   
                 R D120   
                 L C642   
                 R D145   
                 R D42   
               
               
                 L C67   
                 R D67   
                 R D67   
                 L C259   
                 R D4   
                 R D58   
                 L C451   
                 R D50   
                 R D133   
                 L C643   
                 R D145   
                 R D43   
               
               
                 L C68   
                 R D68   
                 R D68   
                 L C260   
                 R D4   
                 R D59   
                 L C452   
                 R D50   
                 R D134   
                 L C644   
                 R D145   
                 R D48   
               
               
                 L C69   
                 R D69   
                 R D69   
                 L C261   
                 R D4   
                 R D78   
                 L C453   
                 R D50   
                 R D135   
                 L C645   
                 R D145   
                 R D49   
               
               
                 L C70   
                 R D70   
                 R D70   
                 L C262   
                 R D4   
                 R D79   
                 L C454   
                 R D50   
                 R D136   
                 L C646   
                 R D145   
                 R D54   
               
               
                 L C71   
                 R D71   
                 R D71   
                 L C263   
                 R D4   
                 R D81   
                 L C455   
                 R D50   
                 R D143   
                 L C647   
                 R D145   
                 R D58   
               
               
                 L C72   
                 R D72   
                 R D72   
                 L C264   
                 R D4   
                 R D87   
                 L C456   
                 R D50   
                 R D144   
                 L C648   
                 R D145   
                 R D59   
               
               
                 L C73   
                 R D73   
                 R D73   
                 L C265   
                 R D4   
                 R D88   
                 L C457   
                 R D50   
                 R D145   
                 L C649   
                 R D145   
                 R D78   
               
               
                 L C74   
                 R D74   
                 R D74   
                 L C266   
                 R D4   
                 R D89   
                 L C458   
                 R D50   
                 R D146   
                 L C650   
                 R D145   
                 R D79   
               
               
                 L C75   
                 R D75   
                 R D75   
                 L C267   
                 R D4   
                 R D93   
                 L C459   
                 R D50   
                 R D147   
                 L C651   
                 R D145   
                 R D81   
               
               
                 L C76   
                 R D76   
                 R D76   
                 L C268   
                 R D4   
                 R D116   
                 L C460   
                 R D50   
                 R D149   
                 L C652   
                 R D145   
                 R D87   
               
               
                 L C77   
                 R D77   
                 R D77   
                 L C269   
                 R D4   
                 R D117   
                 L C461   
                 R D50   
                 R D151   
                 L C653   
                 R D145   
                 R D88   
               
               
                 L C78   
                 R D78   
                 R D78   
                 L C270   
                 R D4   
                 R D118   
                 L C462   
                 R D50   
                 R D154   
                 L C654   
                 R D145   
                 R D89   
               
               
                 L C79   
                 R D79   
                 R D79   
                 L C271   
                 R D4   
                 R D119   
                 L C463   
                 R D55   
                 R D155   
                 L C655   
                 R D145   
                 R D93   
               
               
                 L C80   
                 R D80   
                 R D80   
                 L C272   
                 R D4   
                 R D120   
                 L C464   
                 R D55   
                 R D161   
                 L C656   
                 R D145   
                 R D116   
               
               
                 L C81   
                 R D81   
                 R D81   
                 L C273   
                 R D4   
                 R D133   
                 L C465   
                 R D55   
                 R D175   
                 L C657   
                 R D145   
                 R D117   
               
               
                 L C82   
                 R D82   
                 R D82   
                 L C274   
                 R D4   
                 R D134   
                 L C466   
                 R D55   
                 R D3   
                 L C658   
                 R D145   
                 R D118   
               
               
                 L C83   
                 R D83   
                 R D83   
                 L C275   
                 R D4   
                 R D135   
                 L C467   
                 R D55   
                 R D5   
                 L C659   
                 R D145   
                 R D119   
               
               
                 L C84   
                 R D84   
                 R D84   
                 L C276   
                 R D4   
                 R D136   
                 L C468   
                 R D55   
                 R D18   
                 L C660   
                 R D145   
                 R D120   
               
               
                 L C85   
                 R D85   
                 R D85   
                 L C277   
                 R D4   
                 R D143   
                 L C469   
                 R D55   
                 R D20   
                 L C661   
                 R D145   
                 R D133   
               
               
                 L C86   
                 R D86   
                 R D86   
                 L C278   
                 R D4   
                 R D144   
                 L C470   
                 R D55   
                 R D22   
                 L C662   
                 R D145   
                 R D134   
               
               
                 L C87   
                 R D87   
                 R D87   
                 L C279   
                 R D4   
                 R D145   
                 L C471   
                 R D55   
                 R D37   
                 L C663   
                 R D145   
                 R D135   
               
               
                 L C88   
                 R D88   
                 R D88   
                 L C280   
                 R D4   
                 R D146   
                 L C472   
                 R D55   
                 R D40   
                 L C664   
                 R D145   
                 R D136   
               
               
                 L C89   
                 R D89   
                 R D89   
                 L C281   
                 R D4   
                 R D147   
                 L C473   
                 R D55   
                 R D41   
                 L C665   
                 R D145   
                 R D146   
               
               
                 L C90   
                 R D90   
                 R D90   
                 L C282   
                 R D4   
                 R D149   
                 L C474   
                 R D55   
                 R D42   
                 L C666   
                 R D145   
                 R D147   
               
               
                 L C91   
                 R D91   
                 R D91   
                 L C283   
                 R D4   
                 R D151   
                 L C475   
                 R D55   
                 R D43   
                 L C667   
                 R D145   
                 R D149   
               
               
                 L C92   
                 R D92   
                 R D92   
                 L C284   
                 R D4   
                 R D154   
                 L C476   
                 R D55   
                 R D48   
                 L C668   
                 R D145   
                 R D151   
               
               
                 L C93   
                 R D93   
                 R D93   
                 L C285   
                 R D4   
                 R D155   
                 L C477   
                 R D55   
                 R D49   
                 L C669   
                 R D145   
                 R D154   
               
               
                 L C94   
                 R D94   
                 R D94   
                 L C286   
                 R D4   
                 R D161   
                 L C478   
                 R D55   
                 R D54   
                 L C670   
                 R D145   
                 R D155   
               
               
                 L C95   
                 R D95   
                 R D95   
                 L C287   
                 R D4   
                 R D175   
                 L C479   
                 R D55   
                 R D55   
                 L C671   
                 R D145   
                 R D161   
               
               
                 L C96   
                 R D96   
                 R D96   
                 L C288   
                 R D9   
                 R D3   
                 L C480   
                 R D55   
                 R D59   
                 L C672   
                 R D145   
                 R D175   
               
               
                 L C97   
                 R D97   
                 R D97   
                 L C289   
                 R D9   
                 R D5   
                 L C481   
                 R D55   
                 R D78   
                 L C673   
                 R D146   
                 R D3   
               
               
                 L C98   
                 R D98   
                 R D98   
                 L C290   
                 R D9   
                 R D10   
                 L C482   
                 R D55   
                 R D79   
                 L C674   
                 R D146   
                 R D5   
               
               
                 L C99   
                 R D99   
                 R D99   
                 L C291   
                 R D9   
                 R D17   
                 L C483   
                 R D55   
                 R D81   
                 L C675   
                 R D146   
                 R D17   
               
               
                 L C100   
                 R D100   
                 R D100   
                 L C292   
                 R D9   
                 R D18   
                 L C484   
                 R D55   
                 R D87   
                 L C676   
                 R D146   
                 R D18   
               
               
                 L C101   
                 R D101   
                 R D101   
                 L C293   
                 R D9   
                 R D20   
                 L C485   
                 R D55   
                 R D88   
                 L C677   
                 R D146   
                 R D20   
               
               
                 L C102   
                 R D102   
                 R D102   
                 L C294   
                 R D9   
                 R D22   
                 L C486   
                 R D55   
                 R D89   
                 L C678   
                 R D146   
                 R D22   
               
               
                 L C103   
                 R D103   
                 R D103   
                 L C295   
                 R D9   
                 R D37   
                 L C487   
                 R D55   
                 R D93   
                 L C679   
                 R D146   
                 R D37   
               
               
                 L C104   
                 R D104   
                 R D104   
                 L C296   
                 R D9   
                 R D40   
                 L C488   
                 R D55   
                 R D116   
                 L C680   
                 R D146   
                 R D40   
               
               
                 L C105   
                 R D105   
                 R D105   
                 L C297   
                 R D9   
                 R D41   
                 L C489   
                 R D55   
                 R D117   
                 L C681   
                 R D146   
                 R D41   
               
               
                 L C106   
                 R D106   
                 R D106   
                 L C298   
                 R D9   
                 R D42   
                 L C490   
                 R D55   
                 R D118   
                 L C682   
                 R D146   
                 R D42   
               
               
                 L C107   
                 R D107   
                 R D107   
                 L C299   
                 R D9   
                 R D43   
                 L C491   
                 R D55   
                 R D119   
                 L C683   
                 R D146   
                 R D43   
               
               
                 L C108   
                 R D108   
                 R D108   
                 L C300   
                 R D9   
                 R D48   
                 L C492   
                 R D55   
                 R D120   
                 L C684   
                 R D146   
                 R D48   
               
               
                 L C109   
                 R D109   
                 R D109   
                 L C301   
                 R D9   
                 R D49   
                 L C493   
                 R D55   
                 R D133   
                 L C685   
                 R D146   
                 R D49   
               
               
                 L C110   
                 R D110   
                 R D110   
                 L C302   
                 R D9   
                 R D50   
                 L C494   
                 R D55   
                 R D134   
                 L C686   
                 R D146   
                 R D54   
               
               
                 L C111   
                 R D111   
                 R D111   
                 L C303   
                 R D9   
                 R D54   
                 L C495   
                 R D55   
                 R D135   
                 L C687   
                 R D146   
                 R D58   
               
               
                 L C112   
                 R D112   
                 R D112   
                 L C304   
                 R D9   
                 R D55   
                 L C496   
                 R D55   
                 R D136   
                 L C688   
                 R D146   
                 R D59   
               
               
                 L C113   
                 R D113   
                 R D113   
                 L C305   
                 R D9   
                 R D58   
                 L C497   
                 R D55   
                 R D143   
                 L C689   
                 R D146   
                 R D78   
               
               
                 L C114   
                 R D114   
                 R D114   
                 L C306   
                 R D9   
                 R D59   
                 L C498   
                 R D55   
                 R D144   
                 L C690   
                 R D146   
                 R D79   
               
               
                 L C115   
                 R D115   
                 R D115   
                 L C307   
                 R D9   
                 R D78   
                 L C499   
                 R D55   
                 R D145   
                 L C691   
                 R D146   
                 R D81   
               
               
                 L C116   
                 R D116   
                 R D116   
                 L C308   
                 R D9   
                 R D79   
                 L C500   
                 R D55   
                 R D146   
                 L C692   
                 R D146   
                 R D87   
               
               
                 L C117   
                 R D117   
                 R D117   
                 L C309   
                 R D9   
                 R D81   
                 L C501   
                 R D55   
                 R D147   
                 L C693   
                 R D146   
                 R D88   
               
               
                 L C118   
                 R D118   
                 R D118   
                 L C310   
                 R D9   
                 R D87   
                 L C502   
                 R D55   
                 R D149   
                 L C694   
                 R D146   
                 R D89   
               
               
                 L C119   
                 R D119   
                 R D119   
                 L C311   
                 R D9   
                 R D88   
                 L C503   
                 R D55   
                 R D151   
                 L C695   
                 R D146   
                 R D93   
               
               
                 L C120   
                 R D120   
                 R D120   
                 L C312   
                 R D9   
                 R D89   
                 L C504   
                 R D55   
                 R D154   
                 L C696   
                 R D146   
                 R D117   
               
               
                 L C121   
                 R D121   
                 R D121   
                 L C313   
                 R D9   
                 R D93   
                 L C505   
                 R D55   
                 R D155   
                 L C697   
                 R D146   
                 R D118   
               
               
                 L C122   
                 R D122   
                 R D122   
                 L C314   
                 R D9   
                 R D116   
                 L C506   
                 R D55   
                 R D161   
                 L C698   
                 R D146   
                 R D119   
               
               
                 L C123   
                 R D123   
                 R D123   
                 L C315   
                 R D9   
                 R D117   
                 L C507   
                 R D55   
                 R D175   
                 L C699   
                 R D146   
                 R D120   
               
               
                 L C124   
                 R D124   
                 R D124   
                 L C316   
                 R D9   
                 R D118   
                 L C508   
                 R D116   
                 R D3   
                 L C700   
                 R D146   
                 R D133   
               
               
                 L C125   
                 R D125   
                 R D125   
                 L C317   
                 R D9   
                 R D119   
                 L C509   
                 R D116   
                 R D5   
                 L C701   
                 R D146   
                 R D134   
               
               
                 L C126   
                 R D126   
                 R D126   
                 L C318   
                 R D9   
                 R D120   
                 L C510   
                 R D116   
                 R D17   
                 L C702   
                 R D146   
                 R D135   
               
               
                 L C127   
                 R D127   
                 R D127   
                 L C319   
                 R D9   
                 R D133   
                 L C511   
                 R D116   
                 R D18   
                 L C703   
                 R D146   
                 R D136   
               
               
                 L C128   
                 R D128   
                 R D128   
                 L C320   
                 R D9   
                 R D134   
                 L C512   
                 R D116   
                 R D20   
                 L C704   
                 R D146   
                 R D146   
               
               
                 L C129   
                 R D129   
                 R D129   
                 L C321   
                 R D9   
                 R D135   
                 L C513   
                 R D116   
                 R D22   
                 L C705   
                 R D146   
                 R D147   
               
               
                 L C130   
                 R D130   
                 R D130   
                 L C322   
                 R D9   
                 R D136   
                 L C514   
                 R D116   
                 R D37   
                 L C706   
                 R D146   
                 R D149   
               
               
                 L C131   
                 R D131   
                 R D131   
                 L C323   
                 R D9   
                 R D143   
                 L C515   
                 R D116   
                 R D40   
                 L C707   
                 R D146   
                 R D151   
               
               
                 L C132   
                 R D132   
                 R D132   
                 L C324   
                 R D9   
                 R D144   
                 L C516   
                 R D116   
                 R D41   
                 L C708   
                 R D146   
                 R D154   
               
               
                 L C133   
                 R D133   
                 R D133   
                 L C325   
                 R D9   
                 R D145   
                 L C517   
                 R D116   
                 R D42   
                 L C709   
                 R D146   
                 R D155   
               
               
                 L C134   
                 R D134   
                 R D134   
                 L C326   
                 R D9   
                 R D146   
                 L C518   
                 R D116   
                 R D43   
                 L C710   
                 R D146   
                 R D161   
               
               
                 L C135   
                 R D135   
                 R D135   
                 L C327   
                 R D9   
                 R D147   
                 L C519   
                 R D116   
                 R D48   
                 L C711   
                 R D146   
                 R D175   
               
               
                 L C136   
                 R D136   
                 R D136   
                 L C328   
                 R D9   
                 R D149   
                 L C520   
                 R D116   
                 R D49   
                 L C712   
                 R D133   
                 R D3   
               
               
                 L C137   
                 R D137   
                 R D137   
                 L C329   
                 R D9   
                 R D151   
                 L C521   
                 R D116   
                 R D54   
                 L C713   
                 R D133   
                 R D5   
               
               
                 L C138   
                 R D138   
                 R D138   
                 L C330   
                 R D9   
                 R D154   
                 L C522   
                 R D116   
                 R D55   
                 L C714   
                 R D133   
                 R D3   
               
               
                 L C139   
                 R D139   
                 R D139   
                 L C331   
                 R D9   
                 R D155   
                 L C523   
                 R D116   
                 R D59   
                 L C715   
                 R D133   
                 R D18   
               
               
                 L C140   
                 R D140   
                 R D140   
                 L C332   
                 R D9   
                 R D161   
                 L C524   
                 R D116   
                 R D78   
                 L C716   
                 R D133   
                 R D20   
               
               
                 L C141   
                 R D141   
                 R D141   
                 L C333   
                 R D9   
                 R D175   
                 L C525   
                 R D116   
                 R D79   
                 L C717   
                 R D133   
                 R D22   
               
               
                 L C142   
                 R D142   
                 R D142   
                 L C334   
                 R D10   
                 R D3   
                 L C526   
                 R D116   
                 R D81   
                 L C718   
                 R D133   
                 R D37   
               
               
                 L C143   
                 R D143   
                 R D143   
                 L C335   
                 R D10   
                 R D5   
                 L C527   
                 R D116   
                 R D87   
                 L C719   
                 R D133   
                 R D40   
               
               
                 L C144   
                 R D144   
                 R D144   
                 L C336   
                 R D10   
                 R D17   
                 L C528   
                 R D116   
                 R D88   
                 L C720   
                 R D133   
                 R D41   
               
               
                 L C145   
                 R D145   
                 R D145   
                 L C337   
                 R D10   
                 R D18   
                 L C529   
                 R D116   
                 R D89   
                 L C721   
                 R D133   
                 R D42   
               
               
                 L C146   
                 R D146   
                 R D146   
                 L C338   
                 R D10   
                 R D20   
                 L C530   
                 R D116   
                 R D93   
                 L C722   
                 R D133   
                 R D43   
               
               
                 L C147   
                 R D147   
                 R D147   
                 L C339   
                 R D10   
                 R D22   
                 L C531   
                 R D116   
                 R D117   
                 L C723   
                 R D133   
                 R D48   
               
               
                 L C148   
                 R D148   
                 R D148   
                 L C340   
                 R D10   
                 R D37   
                 L C532   
                 R D116   
                 R D118   
                 L C724   
                 R D133   
                 R D49   
               
               
                 L C149   
                 R D149   
                 R D149   
                 L C341   
                 R D10   
                 R D40   
                 L C533   
                 R D116   
                 R D119   
                 L C725   
                 R D133   
                 R D54   
               
               
                 L C150   
                 R D150   
                 R D150   
                 L C342   
                 R D10   
                 R D41   
                 L C534   
                 R D116   
                 R D120   
                 L C726   
                 R D133   
                 R D58   
               
               
                 L C151   
                 R D151   
                 R D151   
                 L C343   
                 R D10   
                 R D42   
                 L C535   
                 R D116   
                 R D133   
                 L C727   
                 R D133   
                 R D59   
               
               
                 L C152   
                 R D152   
                 R D152   
                 L C344   
                 R D10   
                 R D43   
                 L C536   
                 R D116   
                 R D134   
                 L C728   
                 R D133   
                 R D78   
               
               
                 L C153   
                 R D153   
                 R D153   
                 L C345   
                 R D10   
                 R D48   
                 L C537   
                 R D116   
                 R D135   
                 L C729   
                 R D133   
                 R D79   
               
               
                 L C154   
                 R D154   
                 R D154   
                 L C346   
                 R D10   
                 R D49   
                 L C538   
                 R D116   
                 R D136   
                 L C730   
                 R D133   
                 R D81   
               
               
                 L C155   
                 R D155   
                 R D155   
                 L C347   
                 R D10   
                 R D50   
                 L C539   
                 R D116   
                 R D143   
                 L C731   
                 R D133   
                 R D87   
               
               
                 L C156   
                 R D156   
                 R D156   
                 L C348   
                 R D10   
                 R D54   
                 L C540   
                 R D116   
                 R D144   
                 L C732   
                 R D133   
                 R D88   
               
               
                 L C157   
                 R D157   
                 R D157   
                 L C349   
                 R D10   
                 R D55   
                 L C541   
                 R D116   
                 R D145   
                 L C733   
                 R D133   
                 R D89   
               
               
                 L C158   
                 R D158   
                 R D158   
                 L C350   
                 R D10   
                 R D58   
                 L C542   
                 R D116   
                 R D146   
                 L C734   
                 R D133   
                 R D93   
               
               
                 L C159   
                 R D159   
                 R D159   
                 L C351   
                 R D10   
                 R D59   
                 L C543   
                 R D116   
                 R D147   
                 L C735   
                 R D133   
                 R D117   
               
               
                 L C160   
                 R D160   
                 R D160   
                 L C352   
                 R D10   
                 R D78   
                 L C544   
                 R D116   
                 R D149   
                 L C736   
                 R D133   
                 R D118   
               
               
                 L C161   
                 R D161   
                 R D161   
                 L C353   
                 R D10   
                 R D79   
                 L C545   
                 R D116   
                 R D151   
                 L C737   
                 R D133   
                 R D119   
               
               
                 L C162   
                 R D162   
                 R D162   
                 L C354   
                 R D10   
                 R D81   
                 L C546   
                 R D116   
                 R D154   
                 L C738   
                 R D133   
                 R D120   
               
               
                 L C163   
                 R D163   
                 R D163   
                 L C355   
                 R D10   
                 R D87   
                 L C547   
                 R D116   
                 R D155   
                 L C739   
                 R D133   
                 R D133   
               
               
                 L C164   
                 R D164   
                 R D164   
                 L C356   
                 R D10   
                 R D88   
                 L C548   
                 R D116   
                 R D161   
                 L C740   
                 R D133   
                 R D134   
               
               
                 L C165   
                 R D165   
                 R D165   
                 L C357   
                 R D10   
                 R D89   
                 L C549   
                 R D116   
                 R D175   
                 L C741   
                 R D133   
                 R D135   
               
               
                 L C166   
                 R D166   
                 R D166   
                 L C358   
                 R D10   
                 R D93   
                 L C550   
                 R D143   
                 R D3   
                 L C742   
                 R D133   
                 R D136   
               
               
                 L C167   
                 R D167   
                 R D167   
                 L C359   
                 R D10   
                 R D116   
                 L C551   
                 R D143   
                 R D5   
                 L C743   
                 R D133   
                 R D146   
               
               
                 L C168   
                 R D168   
                 R D168   
                 L C360   
                 R D10   
                 R D117   
                 L C552   
                 R D143   
                 R D17   
                 L C744   
                 R D133   
                 R D147   
               
               
                 L C169   
                 R D169   
                 R D169   
                 L C361   
                 R D10   
                 R D118   
                 L C553   
                 R D143   
                 R D18   
                 L C745   
                 R D133   
                 R D149   
               
               
                 L C170   
                 R D170   
                 R D170   
                 L C362   
                 R D10   
                 R D119   
                 L C554   
                 R D143   
                 R D20   
                 L C746   
                 R D133   
                 R D151   
               
               
                 L C171   
                 R D171   
                 R D171   
                 L C363   
                 R D10   
                 R D120   
                 L C555   
                 R D143   
                 R D22   
                 L C747   
                 R D133   
                 R D154   
               
               
                 L C172   
                 R D172   
                 R D172   
                 L C364   
                 R D10   
                 R D133   
                 L C556   
                 R D143   
                 R D37   
                 L C748   
                 R D133   
                 R D155   
               
               
                 L C173   
                 R D173   
                 R D173   
                 L C365   
                 R D10   
                 R D134   
                 L C557   
                 R D143   
                 R D40   
                 L C749   
                 R D133   
                 R D161   
               
               
                 L C174   
                 R D174   
                 R D174   
                 L C366   
                 R D10   
                 R D135   
                 L C558   
                 R D143   
                 R D41   
                 L C750   
                 R D133   
                 R D175   
               
               
                 L C175   
                 R D175   
                 R D175   
                 L C367   
                 R D10   
                 R D136   
                 L C559   
                 R D143   
                 R D42   
                 L C751   
                 R D175   
                 R D3   
               
               
                 L C176   
                 R D176   
                 R D176   
                 L C368   
                 R D10   
                 R D143   
                 L C560   
                 R D143   
                 R D43   
                 L C752   
                 R D175   
                 R D5   
               
               
                 L C177   
                 R D177   
                 R D177   
                 L C369   
                 R D10   
                 R D144   
                 L C561   
                 R D143   
                 R D48   
                 L C753   
                 R D175   
                 R D18   
               
               
                 L C178   
                 R D178   
                 R D178   
                 L C370   
                 R D10   
                 R D145   
                 L C562   
                 R D143   
                 R D49   
                 L C754   
                 R D175   
                 R D20   
               
               
                 L C179   
                 R D179   
                 R D179   
                 L C371   
                 R D10   
                 R D146   
                 L C563   
                 R D143   
                 R D54   
                 L C755   
                 R D175   
                 R D22   
               
               
                 L C180   
                 R D180   
                 R D180   
                 L C372   
                 R D10   
                 R D147   
                 L C564   
                 R D143   
                 R D58   
                 L C756   
                 R D175   
                 R D37   
               
               
                 L C181   
                 R D181   
                 R D181   
                 L C373   
                 R D10   
                 R D149   
                 L C565   
                 R D143   
                 R D59   
                 L C757   
                 R D175   
                 R D40   
               
               
                 L C182   
                 R D182   
                 R D182   
                 L C374   
                 R D10   
                 R D151   
                 L C566   
                 R D143   
                 R D78   
                 L C758   
                 R D175   
                 R D41   
               
               
                 L C183   
                 R D183   
                 R D183   
                 L C375   
                 R D10   
                 R D154   
                 L C567   
                 R D143   
                 R D79   
                 L C759   
                 R D175   
                 R D42   
               
               
                 L C184   
                 R D184   
                 R D184   
                 L C376   
                 R D10   
                 R D155   
                 L C568   
                 R D143   
                 R D81   
                 L C760   
                 R D175   
                 R D43   
               
               
                 L C185   
                 R D185   
                 R D185   
                 L C377   
                 R D10   
                 R D161   
                 L C569   
                 R D143   
                 R D87   
                 L C761   
                 R D175   
                 R D48   
               
               
                 L C186   
                 R D186   
                 R D186   
                 L C378   
                 R D10   
                 R D175   
                 L C570   
                 R D143   
                 R D88   
                 L C762   
                 R D175   
                 R D49   
               
               
                 L C187   
                 R D187   
                 R D187   
                 L C379   
                 R D17   
                 R D3   
                 L C571   
                 R D143   
                 R D89   
                 L C763   
                 R D175   
                 R D54   
               
               
                 L C188   
                 R D188   
                 R D188   
                 L C380   
                 R D17   
                 R D5   
                 L C572   
                 R D143   
                 R D93   
                 L C764   
                 R D175   
                 R D58   
               
               
                 L C189   
                 R D189   
                 R D189   
                 L C381   
                 R D17   
                 R D18   
                 L C573   
                 R D143   
                 R D116   
                 L C765   
                 R D175   
                 R D59   
               
               
                 L C190   
                 R D190   
                 R D190   
                 L C382   
                 R D17   
                 R D20   
                 L C574   
                 R D143   
                 R D117   
                 L C766   
                 R D175   
                 R D78   
               
               
                 L C191   
                 R D191   
                 R D191   
                 L C383   
                 R D17   
                 R D22   
                 L C575   
                 R D143   
                 R D118   
                 L C767   
                 R D175   
                 R D79   
               
               
                 L C192   
                 R D192   
                 R D192   
                 L C384   
                 R D17   
                 R D37   
                 L C576   
                 R D143   
                 R D119   
                 L C768   
                 R D175   
                 R D81   
               
               
                 L C769   
                 R D193   
                 R D193   
                 L C877   
                 R D1   
                 R D193   
                 L C985   
                 R D4   
                 R D193   
                 L C1093   
                 R D9   
                 R D193   
               
               
                 L C770   
                 R D194   
                 R D194   
                 L C878   
                 R D1   
                 R D194   
                 L C986   
                 R D4   
                 R D194   
                 L C1094   
                 R D9   
                 R D194   
               
               
                 L C771   
                 R D195   
                 R D195   
                 L C879   
                 R D1   
                 R D195   
                 L C987   
                 R D4   
                 R D195   
                 L C1095   
                 R D9   
                 R D195   
               
               
                 L C772   
                 R D196   
                 R D196   
                 L C880   
                 R D1   
                 R D196   
                 L C988   
                 R D4   
                 R D196   
                 L C1096   
                 R D9   
                 R D196   
               
               
                 L C773   
                 R D197   
                 R D197   
                 L C881   
                 R D1   
                 R D197   
                 L C989   
                 R D4   
                 R D197   
                 L C1097   
                 R D9   
                 R D197   
               
               
                 L C774   
                 R D198   
                 R D198   
                 L C882   
                 R D1   
                 R D198   
                 L C990   
                 R D4   
                 R D198   
                 L C1098   
                 R D9   
                 R D198   
               
               
                 L C775   
                 R D199   
                 R D199   
                 L C883   
                 R D1   
                 R D199   
                 L C991   
                 R D4   
                 R D199   
                 L C1099   
                 R D9   
                 R D199   
               
               
                 L C776   
                 R D200   
                 R D200   
                 L C884   
                 R D1   
                 R D200   
                 L C992   
                 R D4   
                 R D200   
                 L C1100   
                 R D9   
                 R D200   
               
               
                 L C777   
                 R D201   
                 R D201   
                 L C885   
                 R D1   
                 R D201   
                 L C993   
                 R D4   
                 R D201   
                 L C1101   
                 R D9   
                 R D201   
               
               
                 L C778   
                 R D202   
                 R D202   
                 L C886   
                 R D1   
                 R D202   
                 L C994   
                 R D4   
                 R D202   
                 L C1102   
                 R D9   
                 R D202   
               
               
                 L C779   
                 R D203   
                 R D203   
                 L C887   
                 R D1   
                 R D203   
                 L C995   
                 R D4   
                 R D203   
                 L C1103   
                 R D9   
                 R D203   
               
               
                 L C780   
                 R D204   
                 R D204   
                 L C888   
                 R D1   
                 R D204   
                 L C996   
                 R D4   
                 R D204   
                 L C1104   
                 R D9   
                 R D204   
               
               
                 L C781   
                 R D205   
                 R D205   
                 L C889   
                 R D1   
                 R D205   
                 L C997   
                 R D4   
                 R D205   
                 L C1105   
                 R D9   
                 R D205   
               
               
                 L C782   
                 R D206   
                 R D206   
                 L C890   
                 R D1   
                 R D206   
                 L C998   
                 R D4   
                 R D206   
                 L C1106   
                 R D9   
                 R D206   
               
               
                 L C783   
                 R D207   
                 R D207   
                 L C891   
                 R D1   
                 R D207   
                 L C999   
                 R D4   
                 R D207   
                 L C1107   
                 R D9   
                 R D207   
               
               
                 L C784   
                 R D208   
                 R D208   
                 L C892   
                 R D1   
                 R D208   
                 L C1000   
                 R D4   
                 R D208   
                 L C1108   
                 R D9   
                 R D208   
               
               
                 L C785   
                 R D209   
                 R D209   
                 L C893   
                 R D1   
                 R D209   
                 L C1001   
                 R D4   
                 R D209   
                 L C1109   
                 R D9   
                 R D209   
               
               
                 L C786   
                 R D210   
                 R D210   
                 L C894   
                 R D1   
                 R D210   
                 L C1002   
                 R D4   
                 R D210   
                 L C1110   
                 R D9   
                 R D210   
               
               
                 L C787   
                 R D211   
                 R D211   
                 L C895   
                 R D1   
                 R D211   
                 L C1003   
                 R D4   
                 R D211   
                 L C1111   
                 R D9   
                 R D211   
               
               
                 L C788   
                 R D212   
                 R D212   
                 L C896   
                 R D1   
                 R D212   
                 L C1004   
                 R D4   
                 R D212   
                 L C1112   
                 R D9   
                 R D212   
               
               
                 L C789   
                 R D213   
                 R D213   
                 L C897   
                 R D1   
                 R D213   
                 L C1005   
                 R D4   
                 R D213   
                 L C1113   
                 R D9   
                 R D213   
               
               
                 L C790   
                 R D214   
                 R D214   
                 L C898   
                 R D1   
                 R D214   
                 L C1006   
                 R D4   
                 R D214   
                 L C1114   
                 R D9   
                 R D214   
               
               
                 L C791   
                 R D215   
                 R D215   
                 L C899   
                 R D1   
                 R D215   
                 L C1007   
                 R D4   
                 R D215   
                 L C1115   
                 R D9   
                 R D215   
               
               
                 L C792   
                 R D216   
                 R D216   
                 L C900   
                 R D1   
                 R D216   
                 L C1008   
                 R D4   
                 R D216   
                 L C1116   
                 R D9   
                 R D216   
               
               
                 L C793   
                 R D217   
                 R D217   
                 L C901   
                 R D1   
                 R D217   
                 L C1009   
                 R D4   
                 R D217   
                 L C1117   
                 R D9   
                 R D217   
               
               
                 L C794   
                 R D218   
                 R D218   
                 L C902   
                 R D1   
                 R D218   
                 L C1010   
                 R D4   
                 R D218   
                 L C1118   
                 R D9   
                 R D218   
               
               
                 L C795   
                 R D219   
                 R D219   
                 L C903   
                 R D1   
                 R D219   
                 L C1011   
                 R D4   
                 R D219   
                 L C1119   
                 R D9   
                 R D219   
               
               
                 L C796   
                 R D220   
                 R D220   
                 L C904   
                 R D1   
                 R D220   
                 L C1012   
                 R D4   
                 R D220   
                 L C1120   
                 R D9   
                 R D220   
               
               
                 L C797   
                 R D221   
                 R D221   
                 L C905   
                 R D1   
                 R D221   
                 L C1013   
                 R D4   
                 R D221   
                 L C1121   
                 R D9   
                 R D221   
               
               
                 L C798   
                 R D222   
                 R D222   
                 L C906   
                 R D1   
                 R D222   
                 L C1014   
                 R D4   
                 R D222   
                 L C1122   
                 R D9   
                 R D222   
               
               
                 L C799   
                 R D223   
                 R D223   
                 L C907   
                 R D1   
                 R D223   
                 L C1015   
                 R D4   
                 R D223   
                 L C1123   
                 R D9   
                 R D223   
               
               
                 L C800   
                 R D224   
                 R D224   
                 L C908   
                 R D1   
                 R D224   
                 L C1016   
                 R D4   
                 R D224   
                 L C1124   
                 R D9   
                 R D224   
               
               
                 L C801   
                 R D225   
                 R D225   
                 L C909   
                 R D1   
                 R D225   
                 L C1017   
                 R D4   
                 R D225   
                 L C1125   
                 R D9   
                 R D225   
               
               
                 L C802   
                 R D226   
                 R D226   
                 L C910   
                 R D1   
                 R D226   
                 L C1018   
                 R D4   
                 R D226   
                 L C1126   
                 R D9   
                 R D226   
               
               
                 L C803   
                 R D227   
                 R D227   
                 L C911   
                 R D1   
                 R D227   
                 L C1019   
                 R D4   
                 R D227   
                 L C1127   
                 R D9   
                 R D227   
               
               
                 L C804   
                 R D228   
                 R D228   
                 L C912   
                 R D1   
                 R D228   
                 L C1020   
                 R D4   
                 R D228   
                 L C1128   
                 R D9   
                 R D228   
               
               
                 L C805   
                 R D229   
                 R D229   
                 L C913   
                 R D1   
                 R D229   
                 L C1021   
                 R D4   
                 R D229   
                 L C1129   
                 R D9   
                 R D229   
               
               
                 L C806   
                 R D230   
                 R D230   
                 L C914   
                 R D1   
                 R D230   
                 L C1022   
                 R D4   
                 R D230   
                 L C1130   
                 R D9   
                 R D230   
               
               
                 L C807   
                 R D231   
                 R D231   
                 L C915   
                 R D1   
                 R D231   
                 L C1023   
                 R D4   
                 R D231   
                 L C1131   
                 R D9   
                 R D231   
               
               
                 L C808   
                 R D232   
                 R D232   
                 L C916   
                 R D1   
                 R D232   
                 L C1024   
                 R D4   
                 R D232   
                 L C1132   
                 R D9   
                 R D232   
               
               
                 L C809   
                 R D233   
                 R D233   
                 L C917   
                 R D1   
                 R D233   
                 L C1025   
                 R D4   
                 R D233   
                 L C1133   
                 R D9   
                 R D233   
               
               
                 L C810   
                 R D234   
                 R D234   
                 L C918   
                 R D1   
                 R D234   
                 L C1026   
                 R D4   
                 R D234   
                 L C1134   
                 R D9   
                 R D234   
               
               
                 L C811   
                 R D235   
                 R D235   
                 L C919   
                 R D1   
                 R D235   
                 L C1027   
                 R D4   
                 R D235   
                 L C1135   
                 R D9   
                 R D235   
               
               
                 L C812   
                 R D236   
                 R D236   
                 L C920   
                 R D1   
                 R D236   
                 L C1028   
                 R D4   
                 R D236   
                 L C1136   
                 R D9   
                 R D236   
               
               
                 L C813   
                 R D237   
                 R D237   
                 L C921   
                 R D1   
                 R D237   
                 L C1029   
                 R D4   
                 R D237   
                 L C1137   
                 R D9   
                 R D237   
               
               
                 L C814   
                 R D238   
                 R D238   
                 L C922   
                 R D1   
                 R D238   
                 L C1030   
                 R D4   
                 R D238   
                 L C1138   
                 R D9   
                 R D238   
               
               
                 L C815   
                 R D239   
                 R D239   
                 L C923   
                 R D1   
                 R D239   
                 L C1031   
                 R D4   
                 R D239   
                 L C1139   
                 R D9   
                 R D239   
               
               
                 L C816   
                 R D240   
                 R D240   
                 L C924   
                 R D1   
                 R D240   
                 L C1032   
                 R D4   
                 R D240   
                 L C1140   
                 R D9   
                 R D240   
               
               
                 L C817   
                 R D241   
                 R D241   
                 L C925   
                 R D1   
                 R D241   
                 L C1033   
                 R D4   
                 R D241   
                 L C1141   
                 R D9   
                 R D241   
               
               
                 L C818   
                 R D242   
                 R D242   
                 L C926   
                 R D1   
                 R D242   
                 L C1034   
                 R D4   
                 R D242   
                 L C1142   
                 R D9   
                 R D242   
               
               
                 L C819   
                 R D243   
                 R D243   
                 L C927   
                 R D1   
                 R D243   
                 L C1035   
                 R D4   
                 R D243   
                 L C1143   
                 R D9   
                 R D243   
               
               
                 L C820   
                 R D244   
                 R D244   
                 L C928   
                 R D1   
                 R D244   
                 L C1036   
                 R D4   
                 R D244   
                 L C1144   
                 R D9   
                 R D244   
               
               
                 L C821   
                 R D245   
                 R D245   
                 L C929   
                 R D1   
                 R D245   
                 L C1037   
                 R D4   
                 R D245   
                 L C1145   
                 R D9   
                 R D245   
               
               
                 L C822   
                 R D246   
                 R D246   
                 L C930   
                 R D1   
                 R D246   
                 L C1038   
                 R D4   
                 R D246   
                 L C1146   
                 R D9   
                 R D246   
               
               
                 L C823   
                 R D17   
                 R D193   
                 L C931   
                 R D50   
                 R D193   
                 L C1039   
                 R D145   
                 R D193   
                 L C1147   
                 R D168   
                 R D193   
               
               
                 L C824   
                 R D17   
                 R D194   
                 L C932   
                 R D50   
                 R D194   
                 L C1040   
                 R D145   
                 R D194   
                 L C1148   
                 R D168   
                 R D194   
               
               
                 L C825   
                 R D17   
                 R D195   
                 L C933   
                 R D50   
                 R D195   
                 L C1041   
                 R D145   
                 R D195   
                 L C1149   
                 R D168   
                 R D195   
               
               
                 L C826   
                 R D17   
                 R D196   
                 L C934   
                 R D50   
                 R D196   
                 L C1042   
                 R D145   
                 R D196   
                 L C1150   
                 R D168   
                 R D196   
               
               
                 L C827   
                 R D17   
                 R D197   
                 L C935   
                 R D50   
                 R D197   
                 L C1043   
                 R D145   
                 R D197   
                 L C1151   
                 R D168   
                 R D197   
               
               
                 L C828   
                 R D17   
                 R D198   
                 L C936   
                 R D50   
                 R D198   
                 L C1044   
                 R D145   
                 R D198   
                 L C1152   
                 R D168   
                 R D198   
               
               
                 L C829   
                 R D17   
                 R D199   
                 L C937   
                 R D50   
                 R D199   
                 L C1045   
                 R D145   
                 R D199   
                 L C1153   
                 R D168   
                 R D199   
               
               
                 L C830   
                 R D17   
                 R D200   
                 L C938   
                 R D50   
                 R D200   
                 L C1046   
                 R D145   
                 R D200   
                 L C1154   
                 R D168   
                 R D200   
               
               
                 L C831   
                 R D17   
                 R D201   
                 L C939   
                 R D50   
                 R D201   
                 L C1047   
                 R D145   
                 R D201   
                 L C1155   
                 R D168   
                 R D201   
               
               
                 L C832   
                 R D17   
                 R D202   
                 L C940   
                 R D50   
                 R D202   
                 L C1048   
                 R D145   
                 R D202   
                 L C1156   
                 R D168   
                 R D202   
               
               
                 L C833   
                 R D17   
                 R D203   
                 L C941   
                 R D50   
                 R D203   
                 L C1049   
                 R D145   
                 R D203   
                 L C1157   
                 R D168   
                 R D203   
               
               
                 L C834   
                 R D17   
                 R D204   
                 L C942   
                 R D50   
                 R D204   
                 L C1050   
                 R D145   
                 R D204   
                 L C1158   
                 R D168   
                 R D204   
               
               
                 L C835   
                 R D17   
                 R D205   
                 L C943   
                 R D50   
                 R D205   
                 L C1051   
                 R D145   
                 R D205   
                 L C1159   
                 R D168   
                 R D205   
               
               
                 L C836   
                 R D17   
                 R D206   
                 L C944   
                 R D50   
                 R D206   
                 L C1052   
                 R D145   
                 R D206   
                 L C1160   
                 R D168   
                 R D206   
               
               
                 L C837   
                 R D17   
                 R D207   
                 L C945   
                 R D50   
                 R D207   
                 L C1053   
                 R D145   
                 R D207   
                 L C1161   
                 R D168   
                 R D207   
               
               
                 L C838   
                 R D17   
                 R D208   
                 L C946   
                 R D50   
                 R D208   
                 L C1054   
                 R D145   
                 R D208   
                 L C1162   
                 R D168   
                 R D208   
               
               
                 L C839   
                 R D17   
                 R D209   
                 L C947   
                 R D50   
                 R D209   
                 L C1055   
                 R D145   
                 R D209   
                 L C1163   
                 R D168   
                 R D209   
               
               
                 L C840   
                 R D17   
                 R D210   
                 L C948   
                 R D50   
                 R D210   
                 L C1056   
                 R D145   
                 R D210   
                 L C1164   
                 R D168   
                 R D210   
               
               
                 L C841   
                 R D17   
                 R D211   
                 L C949   
                 R D50   
                 R D211   
                 L C1057   
                 R D145   
                 R D211   
                 L C1165   
                 R D168   
                 R D211   
               
               
                 L C842   
                 R D17   
                 R D212   
                 L C950   
                 R D50   
                 R D212   
                 L C1058   
                 R D145   
                 R D212   
                 L C1166   
                 R D168   
                 R D212   
               
               
                 L C843   
                 R D17   
                 R D213   
                 L C951   
                 R D50   
                 R D213   
                 L C1059   
                 R D145   
                 R D213   
                 L C1167   
                 R D168   
                 R D213   
               
               
                 L C844   
                 R D17   
                 R D214   
                 L C952   
                 R D50   
                 R D214   
                 L C1060   
                 R D145   
                 R D214   
                 L C1168   
                 R D168   
                 R D214   
               
               
                 L C845   
                 R D17   
                 R D215   
                 L C953   
                 R D50   
                 R D215   
                 L C1061   
                 R D145   
                 R D215   
                 L C1169   
                 R D168   
                 R D215   
               
               
                 L C846   
                 R D17   
                 R D216   
                 L C954   
                 R D50   
                 R D216   
                 L C1062   
                 R D145   
                 R D216   
                 L C1170   
                 R D168   
                 R D216   
               
               
                 L C847   
                 R D17   
                 R D217   
                 L C955   
                 R D50   
                 R D217   
                 L C1063   
                 R D145   
                 R D217   
                 L C1171   
                 R D168   
                 R D217   
               
               
                 L C848   
                 R D17   
                 R D218   
                 L C956   
                 R D50   
                 R D218   
                 L C1064   
                 R D145   
                 R D218   
                 L C1172   
                 R D168   
                 R D218   
               
               
                 L C849   
                 R D17   
                 R D219   
                 L C957   
                 R D50   
                 R D219   
                 L C1065   
                 R D145   
                 R D219   
                 L C1173   
                 R D168   
                 R D219   
               
               
                 L C850   
                 R D17   
                 R D220   
                 L C958   
                 R D50   
                 R D220   
                 L C1066   
                 R D145   
                 R D220   
                 L C1174   
                 R D168   
                 R D220   
               
               
                 L C851   
                 R D17   
                 R D221   
                 L C959   
                 R D50   
                 R D221   
                 L C1067   
                 R D145   
                 R D221   
                 L C1175   
                 R D168   
                 R D221   
               
               
                 L C852   
                 R D17   
                 R D222   
                 L C960   
                 R D50   
                 R D222   
                 L C1068   
                 R D145   
                 R D222   
                 L C1176   
                 R D168   
                 R D222   
               
               
                 L C853   
                 R D17   
                 R D223   
                 L C961   
                 R D50   
                 R D223   
                 L C1069   
                 R D145   
                 R D223   
                 L C1177   
                 R D168   
                 R D223   
               
               
                 L C854   
                 R D17   
                 R D224   
                 L C962   
                 R D50   
                 R D224   
                 L C1070   
                 R D145   
                 R D224   
                 L C1178   
                 R D168   
                 R D224   
               
               
                 L C855   
                 R D17   
                 R D225   
                 L C963   
                 R D50   
                 R D225   
                 L C1071   
                 R D145   
                 R D225   
                 L C1179   
                 R D168   
                 R D225   
               
               
                 L C856   
                 R D17   
                 R D226   
                 L C964   
                 R D50   
                 R D226   
                 L C1072   
                 R D145   
                 R D226   
                 L C1180   
                 R D168   
                 R D226   
               
               
                 L C857   
                 R D17   
                 R D227   
                 L C965   
                 R D50   
                 R D227   
                 L C1073   
                 R D145   
                 R D227   
                 L C1181   
                 R D168   
                 R D227   
               
               
                 L C858   
                 R D17   
                 R D228   
                 L C966   
                 R D50   
                 R D228   
                 L C1074   
                 R D145   
                 R D228   
                 L C1182   
                 R D168   
                 R D228   
               
               
                 L C859   
                 R D17   
                 R D229   
                 L C967   
                 R D50   
                 R D229   
                 L C1075   
                 R D145   
                 R D229   
                 L C1183   
                 R D168   
                 R D229   
               
               
                 L C860   
                 R D17   
                 R D230   
                 L C968   
                 R D50   
                 R D230   
                 L C1076   
                 R D145   
                 R D230   
                 L C1184   
                 R D168   
                 R D230   
               
               
                 L C861   
                 R D17   
                 R D231   
                 L C969   
                 R D50   
                 R D231   
                 L C1077   
                 R D145   
                 R D231   
                 L C1185   
                 R D168   
                 R D231   
               
               
                 L C862   
                 R D17   
                 R D232   
                 L C970   
                 R D50   
                 R D232   
                 L C1078   
                 R D145   
                 R D232   
                 L C1186   
                 R D168   
                 R D232   
               
               
                 L C863   
                 R D17   
                 R D233   
                 L C971   
                 R D50   
                 R D233   
                 L C1079   
                 R D145   
                 R D233   
                 L C1187   
                 R D168   
                 R D233   
               
               
                 L C864   
                 R D17   
                 R D234   
                 L C972   
                 R D50   
                 R D234   
                 L C1080   
                 R D145   
                 R D234   
                 L C1188   
                 R D168   
                 R D234   
               
               
                 L C865   
                 R D17   
                 R D235   
                 L C973   
                 R D50   
                 R D235   
                 L C1081   
                 R D145   
                 R D235   
                 L C1189   
                 R D168   
                 R D235   
               
               
                 L C866   
                 R D17   
                 R D236   
                 L C974   
                 R D50   
                 R D236   
                 L C1082   
                 R D145   
                 R D236   
                 L C1190   
                 R D168   
                 R D236   
               
               
                 L C867   
                 R D17   
                 R D237   
                 L C975   
                 R D50   
                 R D237   
                 L C1083   
                 R D145   
                 R D237   
                 L C1191   
                 R D168   
                 R D237   
               
               
                 L C868   
                 R D17   
                 R D238   
                 L C976   
                 R D50   
                 R D238   
                 L C1084   
                 R D145   
                 R D238   
                 L C1192   
                 R D168   
                 R D238   
               
               
                 L C869   
                 R D17   
                 R D239   
                 L C977   
                 R D50   
                 R D239   
                 L C1085   
                 R D145   
                 R D239   
                 L C1193   
                 R D168   
                 R D239   
               
               
                 L C870   
                 R D17   
                 R D240   
                 L C978   
                 R D50   
                 R D240   
                 L C1086   
                 R D145   
                 R D240   
                 L C1194   
                 R D168   
                 R D240   
               
               
                 L C871   
                 R D17   
                 R D241   
                 L C979   
                 R D50   
                 R D241   
                 L C1087   
                 R D145   
                 R D241   
                 L C1195   
                 R D168   
                 R D241   
               
               
                 L C872   
                 R D17   
                 R D242   
                 L C980   
                 R D50   
                 R D242   
                 L C1088   
                 R D145   
                 R D242   
                 L C1196   
                 R D168   
                 R D242   
               
               
                 L C873   
                 R D17   
                 R D243   
                 L C981   
                 R D50   
                 R D243   
                 L C1089   
                 R D145   
                 R D243   
                 L C1197   
                 R D168   
                 R D243   
               
               
                 L C874   
                 R D17   
                 R D244   
                 L C982   
                 R D50   
                 R D244   
                 L C1090   
                 R D145   
                 R D244   
                 L C1198   
                 R D168   
                 R D244   
               
               
                 L C875   
                 R D17   
                 R D245   
                 L C983   
                 R D50   
                 R D245   
                 L C1091   
                 R D145   
                 R D245   
                 L C1199   
                 R D168   
                 R D245   
               
               
                 L C876   
                 R D17   
                 R D246   
                 L C984   
                 R D50   
                 R D246   
                 L C1092   
                 R D145   
                 R D246   
                 L C1200   
                 R D168   
                 R D246   
               
               
                 L C1201   
                 R D10   
                 R D193   
                 L C1255   
                 R D55   
                 R D193   
                 L C1309   
                 R D37   
                 R D193   
                 L C1363   
                 R D143   
                 R D193   
               
               
                 L C1202   
                 R D10   
                 R D194   
                 L C1256   
                 R D55   
                 R D194   
                 L C1310   
                 R D37   
                 R D194   
                 L C1364   
                 R D143   
                 R D194   
               
               
                 L C1203   
                 R D10   
                 R D195   
                 L C1257   
                 R D55   
                 R D195   
                 L C1311   
                 R D37   
                 R D195   
                 L C1365   
                 R D143   
                 R D195   
               
               
                 L C1204   
                 R D10   
                 R D196   
                 L C1258   
                 R D55   
                 R D196   
                 L C1312   
                 R D37   
                 R D196   
                 L C1366   
                 R D143   
                 R D196   
               
               
                 L C1205   
                 R D10   
                 R D197   
                 L C1259   
                 R D55   
                 R D197   
                 L C1313   
                 R D37   
                 R D197   
                 L C1367   
                 R D143   
                 R D197   
               
               
                 L C1206   
                 R D10   
                 R D198   
                 L C1260   
                 R D55   
                 R D198   
                 L C1314   
                 R D37   
                 R D198   
                 L C1368   
                 R D143   
                 R D198   
               
               
                 L C1207   
                 R D10   
                 R D199   
                 L C1261   
                 R D55   
                 R D199   
                 L C1315   
                 R D37   
                 R D199   
                 L C1369   
                 R D143   
                 R D199   
               
               
                 L C1208   
                 R D10   
                 R D200   
                 L C1262   
                 R D55   
                 R D200   
                 L C1316   
                 R D37   
                 R D200   
                 L C1370   
                 R D143   
                 R D200   
               
               
                 L C1209   
                 R D10   
                 R D201   
                 L C1263   
                 R D55   
                 R D201   
                 L C1317   
                 R D37   
                 R D201   
                 L C1371   
                 R D143   
                 R D201   
               
               
                 L C1210   
                 R D10   
                 R D202   
                 L C1264   
                 R D55   
                 R D202   
                 L C1318   
                 R D37   
                 R D202   
                 L C1372   
                 R D143   
                 R D202   
               
               
                 L C1211   
                 R D10   
                 R D203   
                 L C1265   
                 R D55   
                 R D203   
                 L C1319   
                 R D37   
                 R D203   
                 L C1373   
                 R D143   
                 R D203   
               
               
                 L C1212   
                 R D10   
                 R D204   
                 L C1266   
                 R D55   
                 R D204   
                 L C1320   
                 R D37   
                 R D204   
                 L C1374   
                 R D143   
                 R D204   
               
               
                 L C1213   
                 R D10   
                 R D205   
                 L C1267   
                 R D55   
                 R D205   
                 L C1321   
                 R D37   
                 R D205   
                 L C1375   
                 R D143   
                 R D205   
               
               
                 L C1214   
                 R D10   
                 R D206   
                 L C1268   
                 R D55   
                 R D206   
                 L C1322   
                 R D37   
                 R D206   
                 L C1376   
                 R D143   
                 R D206   
               
               
                 L C1215   
                 R D10   
                 R D207   
                 L C1269   
                 R D55   
                 R D207   
                 L C1323   
                 R D37   
                 R D207   
                 L C1377   
                 R D143   
                 R D207   
               
               
                 L C1216   
                 R D10   
                 R D208   
                 L C1270   
                 R D55   
                 R D208   
                 L C1324   
                 R D37   
                 R D208   
                 L C1378   
                 R D143   
                 R D208   
               
               
                 L C1217   
                 R D10   
                 R D209   
                 L C1271   
                 R D55   
                 R D209   
                 L C1325   
                 R D37   
                 R D209   
                 L C1379   
                 R D143   
                 R D209   
               
               
                 L C1218   
                 R D10   
                 R D210   
                 L C1272   
                 R D55   
                 R D210   
                 L C1326   
                 R D37   
                 R D210   
                 L C1380   
                 R D143   
                 R D210   
               
               
                 L C1219   
                 R D10   
                 R D211   
                 L C1273   
                 R D55   
                 R D211   
                 L C1327   
                 R D37   
                 R D211   
                 L C1381   
                 R D143   
                 R D211   
               
               
                 L C1220   
                 R D10   
                 R D212   
                 L C1274   
                 R D55   
                 R D212   
                 L C1328   
                 R D37   
                 R D212   
                 L C1382   
                 R D143   
                 R D212   
               
               
                 L C1221   
                 R D10   
                 R D213   
                 L C1275   
                 R D55   
                 R D213   
                 L C1329   
                 R D37   
                 R D213   
                 L C1383   
                 R D143   
                 R D213   
               
               
                 L C1222   
                 R D10   
                 R D214   
                 L C1276   
                 R D55   
                 R D214   
                 L C1330   
                 R D37   
                 R D214   
                 L C1384   
                 R D143   
                 R D214   
               
               
                 L C1223   
                 R D10   
                 R D215   
                 L C1277   
                 R D55   
                 R D215   
                 L C1331   
                 R D37   
                 R D215   
                 L C1385   
                 R D143   
                 R D215   
               
               
                 L C1224   
                 R D10   
                 R D216   
                 L C1278   
                 R D55   
                 R D216   
                 L C1332   
                 R D37   
                 R D216   
                 L C1386   
                 R D143   
                 R D216   
               
               
                 L C1225   
                 R D10   
                 R D217   
                 L C1279   
                 R D55   
                 R D217   
                 L C1333   
                 R D37   
                 R D217   
                 L C1387   
                 R D143   
                 R D217   
               
               
                 L C1226   
                 R D10   
                 R D218   
                 L C1280   
                 R D55   
                 R D218   
                 L C1334   
                 R D37   
                 R D218   
                 L C1388   
                 R D143   
                 R D218   
               
               
                 L C1227   
                 R D10   
                 R D219   
                 L C1281   
                 R D55   
                 R D219   
                 L C1335   
                 R D37   
                 R D219   
                 L C1389   
                 R D143   
                 R D219   
               
               
                 L C1228   
                 R D10   
                 R D220   
                 L C1282   
                 R D55   
                 R D220   
                 L C1336   
                 R D37   
                 R D220   
                 L C1390   
                 R D143   
                 R D220   
               
               
                 L C1229   
                 R D10   
                 R D221   
                 L C1283   
                 R D55   
                 R D221   
                 L C1337   
                 R D37   
                 R D221   
                 L C1391   
                 R D143   
                 R D221   
               
               
                 L C1230   
                 R D10   
                 R D222   
                 L C1284   
                 R D55   
                 R D222   
                 L C1338   
                 R D37   
                 R D222   
                 L C1392   
                 R D143   
                 R D222   
               
               
                 L C1231   
                 R D10   
                 R D223   
                 L C1285   
                 R D55   
                 R D223   
                 L C1339   
                 R D37   
                 R D223   
                 L C1393   
                 R D143   
                 R D223   
               
               
                 L C1232   
                 R D10   
                 R D224   
                 L C1286   
                 R D55   
                 R D224   
                 L C1340   
                 R D37   
                 R D224   
                 L C1394   
                 R D143   
                 R D224   
               
               
                 L C1233   
                 R D10   
                 R D225   
                 L C1287   
                 R D55   
                 R D225   
                 L C1341   
                 R D37   
                 R D225   
                 L C1395   
                 R D143   
                 R D225   
               
               
                 L C1234   
                 R D10   
                 R D226   
                 L C1288   
                 R D55   
                 R D226   
                 L C1342   
                 R D37   
                 R D226   
                 L C1396   
                 R D143   
                 R D226   
               
               
                 L C1235   
                 R D10   
                 R D227   
                 L C1289   
                 R D55   
                 R D227   
                 L C1343   
                 R D37   
                 R D227   
                 L C1397   
                 R D143   
                 R D227   
               
               
                 L C1236   
                 R D10   
                 R D228   
                 L C1290   
                 R D55   
                 R D228   
                 L C1344   
                 R D37   
                 R D228   
                 L C1398   
                 R D143   
                 R D228   
               
               
                 L C1237   
                 R D10   
                 R D229   
                 L C1291   
                 R D55   
                 R D229   
                 L C1345   
                 R D37   
                 R D229   
                 L C1399   
                 R D143   
                 R D229   
               
               
                 L C1238   
                 R D10   
                 R D230   
                 L C1292   
                 R D55   
                 R D230   
                 L C1346   
                 R D37   
                 R D230   
                 L C1400   
                 R D143   
                 R D230   
               
               
                 L C1239   
                 R D10   
                 R D231   
                 L C1293   
                 R D55   
                 R D231   
                 L C1347   
                 R D37   
                 R D231   
                 L C1401   
                 R D143   
                 R D231   
               
               
                 L C1240   
                 R D10   
                 R D232   
                 L C1294   
                 R D55   
                 R D232   
                 L C1348   
                 R D37   
                 R D232   
                 L C1402   
                 R D143   
                 R D232   
               
               
                 L C1241   
                 R D10   
                 R D233   
                 L C1295   
                 R D55   
                 R D233   
                 L C1349   
                 R D37   
                 R D233   
                 L C1403   
                 R D143   
                 R D233   
               
               
                 L C1242   
                 R D10   
                 R D234   
                 L C1296   
                 R D55   
                 R D234   
                 L C1350   
                 R D37   
                 R D234   
                 L C1404   
                 R D143   
                 R D234   
               
               
                 L C1243   
                 R D10   
                 R D235   
                 L C1297   
                 R D55   
                 R D235   
                 L C1351   
                 R D37   
                 R D235   
                 L C1405   
                 R D143   
                 R D235   
               
               
                 L C1244   
                 R D10   
                 R D236   
                 L C1298   
                 R D55   
                 R D236   
                 L C1352   
                 R D37   
                 R D236   
                 L C1406   
                 R D143   
                 R D236   
               
               
                 L C1245   
                 R D10   
                 R D237   
                 L C1299   
                 R D55   
                 R D237   
                 L C1353   
                 R D37   
                 R D237   
                 L C1407   
                 R D143   
                 R D237   
               
               
                 L C1246   
                 R D10   
                 R D238   
                 L C1300   
                 R D55   
                 R D238   
                 L C1354   
                 R D37   
                 R D238   
                 L C1408   
                 R D143   
                 R D238   
               
               
                 L C1247   
                 R D10   
                 R D239   
                 L C1301   
                 R D55   
                 R D239   
                 L C1355   
                 R D37   
                 R D239   
                 L C1409   
                 R D143   
                 R D239   
               
               
                 L C1248   
                 R D10   
                 R D240   
                 L C1302   
                 R D55   
                 R D240   
                 L C1356   
                 R D37   
                 R D240   
                 L C1410   
                 R D143   
                 R D240   
               
               
                 L C1249   
                 R D10   
                 R D241   
                 L C1303   
                 R D55   
                 R D241   
                 L C1357   
                 R D37   
                 R D241   
                 L C1411   
                 R D143   
                 R D241   
               
               
                 L C1250   
                 R D10   
                 R D242   
                 L C1304   
                 R D55   
                 R D242   
                 L C1358   
                 R D37   
                 R D242   
                 L C1412   
                 R D143   
                 R D242   
               
               
                 L C1251   
                 R D10   
                 R D243   
                 L C1305   
                 R D55   
                 R D243   
                 L C1359   
                 R D37   
                 R D243   
                 L C1413   
                 R D143   
                 R D243   
               
               
                 L C1252   
                 R D10   
                 R D244   
                 L C1306   
                 R D55   
                 R D244   
                 L C1360   
                 R D37   
                 R D244   
                 L C1414   
                 R D143   
                 R D244   
               
               
                 L C1253   
                 R D10   
                 R D245   
                 L C1307   
                 R D55   
                 R D245   
                 L C1361   
                 R D37   
                 R D245   
                 L C1415   
                 R D143   
                 R D245   
               
               
                 L C1254   
                 R D10   
                 R D246   
                 L C1308   
                 R D55   
                 R D246   
                 L C1362   
                 R D37   
                 R D246   
                 L C1416   
                 R D143   
                 R D246   
               
               
                   
               
            
           
         
       
     
     wherein R D1  to R D246  have the structures defined in the following LIST 11: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments, the compound is selected from the group consisting of only those compounds whose L Bk  corresponds to one of the following: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B130 , L B132 , L B134 , L B136 , L B138 , L B140 , L B142 , L B144 , L B156 , L Bi58 , L B160 , L B162 , L B164 , L B168 , L B172 , L B175 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B222 , L B231 , L B233 , L B235 , L B237 , L B240 , L B242 , L B244 , L B246 , L B248 , L B250 , L B252 , L B254 , L B256 , L B258 , L B260 , L B262 , L B264 , L B265 , L B266 , L B267 , L B268 , L B269 , and L B270 . 
     In some embodiments, the compound is selected from the group consisting of only those compounds whose L Bk  corresponds to one of the following: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B126 , L B128 , L B132 , L B136 , L B138 , L B142 , L B156 , L B162 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B231 , L B233 , L B237 , L B264 , L B265 , L B266 , L B267 , L B268 , L B269 , and L B270 . 
     In some embodiments, the compound is selected from the group consisting of only those compounds having L Cj-I  or L Cj-II  ligand whose corresponding R 201  and R 202  are defined to be one of the following structures: R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D18 , R D20 , R D22 , R D37 , R D40 , R D41 , R D42 , R D43 , R D48 , R D49 , R D50 , R D54 , R D55 , R D58 , R D59 , R D78 , R D79 , R D81 , R D87 , R D88 , R D89 , R D93 , R D116 , R D117 , R D118 , R D119 , R D120 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D147 , R D149 , R D151 , R D154 , R D155 , R D161 , R D175 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 . 
     In some embodiments, the compound is selected from the group consisting of only those compounds having L Cj-I  or L Cj-II  ligand whose corresponding R 201  and R 202  are defined to be one of selected from the following structures: R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D22 , R D43 , R D50 , R D78 , R D116 , R D118 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D149 , R D151 , R D154 , R D155 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 . 
     In some embodiments, the compound is selected from the group consisting of only those compounds having one of the following structures for the L Cj-I  ligand: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments, the compound comprising a ligand L A  of Formula I may be selected from the group consisting of the following structures: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein 
     each of X 96  to X 99  is independently C or N; 
     each Y 100  is independently selected from the group consisting of a NR″, O, S, and Se; 
     each of R 10a , R 20a , R 30a , R 40a , and R 50a  independently represents mono substitution, up to the maximum substitutions, or no substitution; 
     each of R, R′, R″, R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , and R 99  is independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and 
     at least one of R 10a , R 20a , R 30a , R 40a , or R 50a  comprises a structure of Formula III 
     
       
         
         
             
             
         
       
     
     wherein L is a bivalent organic linker; 
     Z is Si or Ge; 
     the dashed line of Formula III indicates direct bond to ring A or ring B; and 
     any two R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , and R 99  are optionally joined or fused to form a ring. 
     In some embodiments, the compound is selected from the group consisting of the structures of the following LIST 12: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments, the compound has the structure of Formula II: 
     
       
         
         
             
             
         
       
     
     where: 
     M 1  is Pd or Pt; 
     moieties E and F are each independently monocyclic or polycyclic ring structure comprising 5-membered and/or 6-membered carbocyclic or heterocyclic rings; 
     Z 5  and Z 4  are each independently C or N; 
     K 1 , K 2 , K 3 , and K 4  are each independently selected from the group consisting of a direct bond, O, and S, wherein at least two of K 1 , K 2 , K 3 , and K 4  are direct bonds; 
     L 1 , L 2 , and L 3  are each independently selected from the group consisting of a single bond, absent a bond, O, S, C═NR′, C═CRR′, CRR′, SiRR′, BR, BRR′, and NR, wherein at least one of L 1  and L 2  is present; 
     R E  and R F  each independently represents zero, mono, or up to a maximum allowed number of substitutions to its associated ring; 
     each of R, R′, R E , and R F  is independently a hydrogen or a substituent selected from the group consisting of the Preferred General Substituents; and 
     two adjacent R, R′, R A , R B , R E , and R F  can be joined or fused together to form a ring where chemically feasible. 
     In some embodiments of Formula II, moiety E and moiety F are both 6-membered aromatic rings. 
     In some embodiments of Formula II, moiety F is a 5-membered or 6-membered heteroaromatic ring. 
     In some embodiments of Formula II, L 1  is O or CRR′. 
     In some embodiments of Formula II, Z 4  is N and Z 5  is C. 
     In some embodiments of Formula II, Z 4  is C and Z 5  is N. 
     In some embodiments of Formula II, L 2  is a direct bond. 
     In some embodiments of Formula II, L 2  is NR. 
     In some embodiments of Formula II, each of K 1 , K 2 , K 3 , and K 4  is a direct bond. 
     In some embodiments of Formula II, one of K 1 , K 2 , K 3 , and K 4  is O. 
     In some embodiments, the compound is selected from the group consisting of compounds having the formula of Pt(L A′ )(Ly): 
     
       
         
         
             
             
         
       
     
     wherein L A′  is selected from the group consisting of the structures shown below: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein L y  is selected from the group consisting of the structures shown below: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Wherein each R E , R F , R X , and R Y  is independently selected from the list consisting of: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein: 
     X A  is C or N; and 
     Z A  is O, S, NR or Se; 
     R A1 , R A2  and R A3  represent mono- to maximum possible substitution or no substitution; 
     each R, R A1 , R A2 , and R A3  is independently a hydrogen or a substituent selected from the group consisting of the General Substituents defined herein, and wherein at least one of R A1 , R A2  and R A3  comprises a structure of Formula III or Formula IIIA. 
     In some embodiments, the compound is selected from the group consisting of the compounds having the formula of Pt(L A′ )(Ly): 
     
       
         
         
             
             
         
       
     
     wherein L A′  is selected from the group consisting of the structures shown below: 
     
       
         
           
               
               
             
               
                   
               
               
                 L A′   
                 Structure of L A′   
               
               
                   
               
             
            
               
                 L A′ 1-(Ro)(Rp)(Rq)(Tr), wherein L A′ 1- (R1)(R1)(R1) to L A′ 1- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 2-(Ro)(Rp)(Rq)(Tr), wherein L A′ 2- (R1)(R1)(R1) to L A′ 2- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 3-(Ro)(Rp)(Rq)(Tr), wherein L A′ 3- (R1)(R1)(R1) to L A′ 3- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 4-(Ro)(Rp)(Rq)(Tr), wherein L A′ 4- (R1)(R1)(R1) to L A′ 4- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 5-(Ro)(Rp)(Rq)(Tr), wherein L A′ 5- (R1)(R1)(R1) to L A′ 5- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 6-(Ro)(Rp)(Rq)(Tr), wherein L A′ 6- (R1)(R1)(R1) to L A′ 6- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 7-(Ro)(Rp)(Rq)(Tr), wherein L A′ 7- (R1)(R1)(R1) to L A′ 7- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 8-(Ro)(Rp)(Rq)(Tr), wherein L A′ 8- (R1)(R1)(R1) to L A′ 8- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 9-(Ro)(Rp)(Rq)(Tr), wherein L A′ 9- (R1)(R1)(R1) to L A′ 9- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 10- (Ro)(Rp)(Rq)(Tr), wherein L A′ 10- (R1)(R1)(R1) to L A′ 10- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 11- (Ro)(Rp)(R)(Tr), wherein L A′ 11- (R1)(R1)(R1) to L A′ 11- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 12- (Ro)(Rp)(Rq)(Tr), wherein L A′ 12- (R1)(R1)(R1) to L A′ 12- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 13- (Ro)(Rp)(Rq)(Tr), wherein L A′ 13- (R1)(R1)(R1) to L A′ 13- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 14- (Ro)(Rp)(R)(Tr), wherein L A′ 14- (R1)(R1)(R1) to L A′ 14- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 15- (Ro)(Rp)(Rq)(Tr), wherein L A′ 15- (R1)(R1)(R1) to L A′ 15- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 16- (Ro)(Rp)(Rq)(Tr), wherein L A′ 16- (R1)(R1)(R1) to L A′ 16- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 17- (Ro)(Rp)(Rq)(Tr), wherein L A′ 17- (R1)(R1)(R1) to L A′ 17- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 18- (Ro)(Rp)(Rq)(Tr), wherein L A′ 18- (R1)(R1)(R1) to L A′ 18- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 19- (Ro)(Rp)(Rq)(Tr), wherein L A′ 19- (R1)(R1)(R1) to L A′ 19- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 20- (Ro)(Rp)(Rq)(Tr), wherein L A′ 20- (R1)(R1)(R1) to L A′ 20- (R135)(R135)(R135), having the structure  
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 21- (Ro)(Rp)(Rq)(Tr), wherein L A′ 21- (R1)(R1)(R1) to L A′ 21- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 22- (Ro)(Rp)(Rq)(Tr), wherein L A′ 22- (R1)(R1)(R1) to L A′ 22- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 23- (Ro)(Rp)(Rq)(Tr), wherein L A′ 23- (R1)(R1)(R1) to L A′ 23- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 24- (Ro)(Rp)(Rq)(Tr), wherein L A′ 24- (R1)(R1)(R1) to L A′ 24- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 25- (Ro)(Rp)(Rq)(Tr), wherein L A′ 25- (R1)(R1)(R1) to L A′ 25- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 26- (Ro)(Rp)(Rq)(Tr), wherein L A′ 26- (R1)(R1)(R1) to L A′ 26- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 27- (Ro)(Rp)(Rq)(Tr), wherein L A′ 27- (R1)(R1)(R1) to L A′ 27- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 28- (Ro)(Rp)(Rq)(Tr), wherein L A′ 28- (R1)(R1)(R1) to L A′ 28- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 29- (Ro)(Rp)(Rq)(Tr), wherein L A′ 29- (R1)(R1)(R1) to L A′ 29- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 30- (Ro)(Rp)(Rq)(Tr), wherein L A′ 30- (R1)(R1)(R1) to L A′ 30- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 31- (Ro)(Rp)(Rq)(Tr), wherein L A′ 31- (R1)(R1)(R1) to L A′ 31- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ -32-(Ro)(Rp)(Rq)(Tr), wherein L A′ 32- (R1)(R1)(R1) to L A′ 32- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 33-(Ro)(Rp)(Rq)(Tr), wherein L A′ 33- (R1)(R1)(R1) to L A′ 33- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 34-(Ro)(Rp)(Rq)(Tr), wherein L A′ 34- (R1)(R1)(R1) to L A′ 34- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 35-(Ro)(Rp)(Rq)(Tr), wherein L A′ 35- (R1)(R1)(R1) to L A′ 35- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 36-(Ro)(Rp)(Rq)(Tr), wherein L A′ 36- (R1)(R1)(R1) to L A′ 36- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 37-(Ro)(Rp)(Rq)(Tr), wherein L A′ 37- (R1)(R1)(R1) to L A′ 37- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 38-(Ro)(Rp)(Rq)(Tr), wherein L A′ 38- (R1)(R1)(R1) to L A′ 38- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 39-(Ro)(Rp)(Rq)(Tr), wherein L A′ 39- (R1)(R1)(R1) to L A′ 39- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 40-(Ro)(Rp)(Rq)(Tr), wherein L A′ 40- (R1)(R1)(R1) to L A′ 40- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 41-(Ro)(Rp)(Rq)(Tr), wherein L A′ 41- (R1)(R1)(R1) to L A′ 41- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 42-(Ro)(Rp)(Rq)(Tr), wherein L A′ 42- (R1)(R1)(R1) to L A′ 42- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 43-(Ro)(Rp)(Rq)(Tr), wherein L A′ 43- (R1)(R1)(R1) to L A′ 43- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 44-(Ro)(Rp)(Rq)(Tr), wherein L A′ 44- (R1)(R1)(R1) to L A′ 44- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 45-(Ro)(Rp)(Rq)(Tr), wherein L A′ 45- (R1)(R1)(R1) to L A′ 45- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 46-(Ro)(Rp)(Rq)(Tr), wherein L A′ 46- (R1)(R1)(R1) to L A′ 46- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 47-(Ro)(Rp)(Rq)(Tr), wherein L A′ 47- (R1)(R1)(R1) to L A′ 47- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 48-(Ro)(Rp)(Rq)(Tr), wherein L A′ 48- (R1)(R1)(R1) to L A′ 48- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 49-(Ro)(Rp)(Rq)(Tr), wherein L A′ 49- (R1)(R1)(R1) to L A′ 49- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 50-(Ro)(Rp)(Rq)(Tr), wherein L A′ 50- (R1)(R1)(R1) to L A′ 50- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 51-(Ro)(Rp)(Rq)(Tr), wherein L A′ 51- (R1)(R1)(R1) to L A′ 51- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 52-(Ro)(Rp)(Rq)(Tr), wherein L A′ 52- (R1)(R1)(R1) to L A′ 52- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 53-(Ro)(Rp)(Rq)(Tr), wherein L A′ 53- (R1)(R1)(R1) to L A′ 53- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 54-(Ro)(Rp)(Rq)(Tr), wherein L A′ 54- (R1)(R1)(R1) to L A′ 54- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 55-(Ro)(Rp)(Rq)(Tr), wherein L A′ 55- (R1)(R1)(R1) to L A′ 55- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 56-(Ro)(Rp)(Rq)(Tr), wherein L A′ 56- (R1)(R1)(R1) to L A′ 56- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 57-(Ro)(Rp)(Rq)(Tr), wherein L A′ 57- (R1)(R1)(R1) to L A′ 57- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 58-(Ro)(Rp)(Rq)(Tr), wherein L A′ 58- (R1)(R1)(R1) to L A′ 58- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 59-(Ro)(Rp)(Rq)(Tr), wherein L A′ 59- (R1)(R1)(R1) to L A′ 59- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 60-(Ro)(Rp)(Rq)(Tr), wherein L A′ 60- (R1)(R1)(R1) to L A′ 60- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 61-(Ro)(Rp)(Rq)(Tr), wherein L A′ 61- (R1)(R1)(R1) to L A′ 61- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 L A′ 62-(Ro)(Rp)(Rq)(Tr), wherein L A′ 62- (R1)(R1)(R1) to L A′ 62- (R135)(R135)(R135), having the structure 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
         
       
     
     wherein L y  is selected from the group consisting of the structures shown below: 
                                 L y     Structure of L y                    L y 1-(Rs)(Rt)(Ru), wherein L y 1- (R1)(R1)(R1) to L y 1- (R135)(R135)(R135), having the structure                                     L y 2-(Rs)(Rt)(Ru), wherein L y 2- (R1)(R1)(R1) to L y 2- (R135)(R135)(R135), having the structure                                     L y 3-(Rs)(Rt)(Ru), wherein L y 3- (R1)(R1)(R1) to L y 3- (R135)(R135)(R135), having the structure                                     L y 4-(Rs)(Rt)(Ru), wherein L y 4- (R1)(R1)(R1) to L y 4- (R135)(R135)(R135), having the structure                                     L y 5-(Rs)(Rt)(Ru), wherein L y 5- (R1)(R1)(R1) to L y 5- (R135)(R135)(R135), having the structure                                      L y 6-(Rs)(Rt)(Ru), wherein L y 6- (R1)(R1)(R1) to L y 6- (R135)(R135)(R135), having the structure                                     L y 7-(Rs)(Rt)(Ru), wherein L y 7- (R1)(R1)(R1) to L y 7- (R135)(R135)(R135), having the structure                                     L y 8-(Rs)(Rt)(Ru), wherein L y 8- (R1)(R1)(R1) to L y 8- (R135)(R135)(R135), having the structure                                     L y 9-(Rs)(Rt)(Ru), wherein L y 9- (R1)(R1)(R1) to L y 9- (R135)(R135)(R135), having the structure                                     L y 10-(Rs)(Rt)(Ru), wherein L y 10- (R1)(R1)(R1) to L y 10- (R135)(R135)(R135), having the structure                                     L y 11-(Rs)(Rt)(Ru), wherein L y 11- (R1)(R1)(R1) to L y 11- (R135)(R135)(R135), having the structure                                     L y 12-(Rs)(Rt)(Ru), wherein L y 12- (R1)(R1)(R1) to L y 12- (R135)(R135)(R135), having the structure                                     L y 13-(Rs)(Rt)(Ru), wherein L y 13-(R1) (R1)( R1) to L y 13- (R135)(R135)(R135), having the structure                                     L y 14-(Rs)(Rt) Ru), wherein L y 14- (R1)(R1)(R1) to L y 14- (R135)(R135)(R135), having the structure                                     L y 15-(Rs)(Rt)(Ru), wherein L y 15- (R1)(R1)(R1) to L y 15- (R135)(R135)(R135), having the structure                                     L y 16-(Rs)(Rt)(Ru), wherein L y 16- (R1)(R1)(R1) to L y 16- (R135)(R135)(R135), having the structure                                     L y 17-(Rs)(Rt)(Ru), wherein L y 17- (R1)(R1)(R1) to L y 17- (R135)(R135)(R135), having the structure                                     L y 18-(Rs)(Rt)(Ru), wherein L y 18- (R1)(R1)(R1) to L y 18- (R135)(R135)(R135), having the structure                                     L y 19-(Rs)(Rt)(Ru), wherein L y 19- (R1)(R1)(R1) to L y 19- (R135)(R135)(R135), having the structure                                     L y 20-(Rs)(Rt)(Ru), wherein L y 20- (R1)(R1)(R1) to L y 20- (R135)(R135)(R135), having the structure                                     L y 21-(Rs)(Rt)(Ru), wherein L y 21- (R1)(R1)(R1) to L y 21- (R135)(R135)(R135), having the structure                                     L y 22-(Rs)(Rt)(Ru), wherein L y 22- (R1)(R1)(R1) to L y 22- (R135)(R135)(R135), having the structure                                     L y 23-(Rs)(Rt)(Ru), wherein L y 23- (R1)(R1)(R1) to L y 23- (R135)(R135)(R135), having the structure                                     L y 24-(Rs)(Rt)(Ru), wherein L y 24- (R1)(R1)(R1) to L y 24- (R135)(R135)(R135), having the structure                                     L y 25-(Rs)(Rt)(Ru), wherein L y 25- (R1)(R1)(R1) to L y 25- (R135)(R135)(R135), having the structure                                     L y 26-(Rs)(Rt)(Ru), wherein L y 26- (R1)(R1)(R1) to L y 26- (R135)(R135)(R135), having the structure                                     L y 27-(Rs)(Rt)(Ru), wherein L y 27- (R1)(R1)(R1) to L y 27- (R135)(R135)(R135), having the structure                                     L y 28-(Rs)(Rt)(Ru), wherein L y 28- (R1)(R1)(R1) to L y 28- (R135)(R135)(R135), having the structure                                     L y 29-(Rs)(Rt)(Ru), wherein L y 29- (R1)(R1)(R1) to L y 29- (R135)(R135)(R135), having the structure                                     L y 30-(Rs)(Rt)(Ru), wherein L y 30- (R1)(R1)(R1) to L y 30- (R135)(R135)(R135), having the structure                                     L y 31-(Rs)(Rt)(Ru), wherein L y 31- (R1)(R1)(R1)toL y 31- (R135) R135)(R135), having the structure                                     L y 32-(Rs)(Rt)(Ru), wherein L y 32- (R1)(R1)(R1) to L y 32- (R135)(R135)(R135), having the structure                                     L y 33-(Rs)(Rt)(Ru), wherein L y 33- (R1)(R1)(R1) to L y 33- (R135)(R135)(R135), having the structure                                          
wherein o, p, q, s, t, and u, are each independently an integer from 1 to 135, and r is an integer from 1 to 28, wherein T1 to T28 have the following structures:
 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein R1 to R135 have the following structures: 
     
       
         
           
               
               
               
               
               
               
             
               
                   
               
               
                   
                 Structure 
                   
                 Structure 
                   
                 Structure 
               
               
                   
               
             
            
               
                 R1 
                 
                   
                     
                     
                         
                         
                     
                   
                 
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     In some embodiments, the compound comprising a ligand of L A  of Formula I may be selected from the group consisting of the following structures: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein: 
     each Y 100  is independently selected from the group consisting of a NR″, O, S, and Se; 
     L is independently selected from the group consisting of a direct bond, BR″, BR″R′″, NR″, PR″, O, S, Se, C═O, C═S, C═Se, C═NR″, C═CR″R′″, S═O, SO 2 , CR″, CR″R′″, SiR″R′″, GeR″R′″, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; 
     X 100  for each occurrence is selected from the group consisting of O, S, Se, NR″, and CR″R′″; 
     each R A″ , R B″ , R C″ , R D″ , R E″ , and R F″  independently represents mono-, up to the maximum substitutions, or no substitutions; 
     each of R, R′, R″, R′″, R A1′ , R A2′ , R A″ , R B″ , R C″ , R D″ , R E″ , R F″ , R G″ , R H″ , R I″ , R J″ , R K″ , R L″ , R M″ , and R N″  is independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, combinations thereof; 
     at least one of R A″ , R B″ , R C″ , R D″ , R E″ , or R F″  comprises a structure of Formula III 
     
       
         
         
             
             
         
       
     
     wherein L is a bivalent organic linker; 
     Z is Si or Ge; 
     the dashed line of Formula III indicates direct bond to ring A or ring B; and 
     any two R, R′, R″, R′″, R A1′ , R A2′ , R A″ , R B″ , R C″ , R D″ , R E″ , R F″ , R G″ , R H″ , R J″ , R I″ , R K″ , R L″ , R M″ , and R N″  may be optionally joined to form a ring. 
     In some embodiments of Formula II, the compound is selected from the group consisting of the structures of the following LIST 13: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In some embodiments, the compound having a formula of M(L A ) p (L B ) q (L C ) r  as described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percent of possible hydrogen atoms (e.g., positions that are hydrogen or deuterium) that are replaced by deuterium atoms. 
     C. The OLEDs and the Devices of the Present Disclosure 
     In another aspect, the present disclosure also provides an OLED device comprising a first organic layer that contains a compound as disclosed in the above compounds section of the present disclosure. 
     In some embodiments, the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer comprises a compound having a formula of M(L A ) p (L B ) q (L C ) r  as described herein. 
     In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant. 
     In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of C n H 2n+1 , OC n H 2n+1 , OAr 1 , N(C n H 2n+1 ) 2 , N(Ar 1 )(Ar 2 ), CH═CH—C n H 2n+1 , C≡CC n H 2n+1 , Ar 1 , Ar 1 —Ar 2 , C n H 2n —Ar 1 , or no substitution, wherein n is from 1 to 10; and wherein Ar 1  and Ar 2  are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. 
     In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5,2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene). 
     In some embodiments, the host may be selected from the HOST Group consisting of: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     and combinations thereof. 
     In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex. 
     In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof. 
     In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure. 
     In some embodiments, the emissive region can comprise a compound having a formula of M(L A ) p (L B ) q (L C ) r  as described herein. 
     In some embodiments, at least one of the anode, the cathode, or a new layer disposed over the organic emissive layer functions as an enhancement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively couples to the emitter material and transfers excited state energy from the emitter material to non-radiative mode of surface plasmon polariton. The enhancement layer is provided no more than a threshold distance away from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the enhancement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on opposite side of the emissive layer from the enhancement layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments this energy is scattered as photons to free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device such as but not limited to the organic waveguide mode, the substrate mode, or another waveguiding mode. If energy is scattered to the non-free space mode of the OLED other outcoupling schemes could be incorporated to extract that energy to free space. In some embodiments, one or more intervening layer can be disposed between the enhancement layer and the outcoupling layer. The examples for interventing layer(s) can be dielectric materials, including organic, inorganic, perovskites, oxides, and may include stacks and/or mixtures of these materials. 
     The enhancement layer modifies the effective properties of the medium in which the emitter material resides resulting in any or all of the following: a decreased rate of emission, a modification of emission line-shape, a change in emission intensity with angle, a change in the stability of the emitter material, a change in the efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placement of the enhancement layer on the cathode side, anode side, or on both sides results in OLED devices which take advantage of any of the above-mentioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure may include any of the other functional layers often found in OLEDs. 
     The enhancement layer can be comprised of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material includes at least one metal. In such embodiments the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials where the medium as a whole acts differently than the sum of its material parts. In particular, we define optically active metamaterials as materials which have both negative permittivity and negative permeability. Hyperbolic metamaterials, on the other hand, are anisotropic media in which the permittivity or permeability are of different sign for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures such as Distributed Bragg Reflectors (“DBRs”) in that the medium should appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology that one skilled in the art can understand: the dielectric constant of the metamaterials in the direction of propagation can be described with the effective medium approximation. Plasmonic materials and metamaterials provide methods for controlling the propagation of light that can enhance OLED performance in a number of ways. 
     In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges. 
     In some embodiments, the outcoupling layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles and in other embodiments the outcoupling layer is composed of a plurality of nanoparticles disposed over a material. In these embodiments the outcoupling may be tunable by at least one of varying a size of the plurality of nanoparticles, varying a shape of the plurality of nanoparticles, changing a material of the plurality of nanoparticles, adjusting a thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, varying a thickness of the enhancement layer, and/or varying the material of the enhancement layer. The plurality of nanoparticles of the device may be formed from at least one of metal, dielectric material, semiconductor materials, an alloy of metal, a mixture of dielectric materials, a stack or layering of one or more materials, and/or a core of one type of material and that is coated with a shell of a different type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layer disposed over them. In some embodiments, the polarization of the emission can be tuned using the outcoupling layer. Varying the dimensionality and periodicity of the outcoupling layer can select a type of polarization that is preferentially outcoupled to air. In some embodiments the outcoupling layer also acts as an electrode of the device. 
     In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compounds section of the present disclosure. 
     In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound having a formula of M(L A ) p (L B ) q (L C ) r  as described herein. 
     In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign. 
     Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable. 
     Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety. 
     The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds. 
     More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference. 
       FIG.  1    shows an organic light emitting device  100 . The figures are not necessarily drawn to scale. Device  100  may include a substrate  110 , an anode  115 , a hole injection layer  120 , a hole transport layer  125 , an electron blocking layer  130 , an emissive layer  135 , a hole blocking layer  140 , an electron transport layer  145 , an electron injection layer  150 , a protective layer  155 , a cathode  160 , and a barrier layer  170 . Cathode  160  is a compound cathode having a first conductive layer  162  and a second conductive layer  164 . Device  100  may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference. 
     More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F 4 -TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. 
       FIG.  2    shows an inverted OLED  200 . The device includes a substrate  210 , a cathode  215 , an emissive layer  220 , a hole transport layer  225 , and an anode  230 . Device  200  may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device  200  has cathode  215  disposed under anode  230 , device  200  may be referred to as an “inverted” OLED. Materials similar to those described with respect to device  100  may be used in the corresponding layers of device  200 .  FIG.  2    provides one example of how some layers may be omitted from the structure of device  100 . 
     The simple layered structure illustrated in  FIGS.  1  and  2    is provided by way of non-limiting example, and it is understood that embodiments of the present disclosure may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device  200 , hole transport layer  225  transports holes and injects holes into emissive layer  220 , and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to  FIGS.  1  and  2   . 
     Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in  FIGS.  1  and  2   . For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties. 
     Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing. 
     Devices fabricated in accordance with embodiments of the present disclosure may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon. 
     Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25° C.), but could be used outside this temperature range, for example, from −40 degree C. to +80° C. 
     More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety. 
     The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures. 
     In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes. 
     In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel. 
     In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments. 
     In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter. 
     According to another aspect, a formulation comprising the compound described herein is also disclosed. 
     The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments. 
     In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein. 
     The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds. 
     D. Combination of the Compounds of the Present Disclosure with Other Materials 
     The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination. 
     a) Conductivity Dopants: 
     A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer. 
     Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012. 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     b) HIL/HTL: 
     A hole injecting/transporting material to be used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO x ; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds. 
     Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures: 
     
       
         
         
             
             
         
       
     
     Each of Ar 1  to Ar 9  is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. 
     In one aspect, Ar 1  to Ar 9  is independently selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
     wherein k is an integer from 1 to 20; X 101  to X 108  is C (including CH) or N; Z 101  is NAr 1 , O, or S; Ar 1  has the same group defined above. 
     Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula: 
     
       
         
         
             
             
         
       
     
     wherein Met is a metal, which can have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 1  and Y 102  are independently selected from C, N, O, P, and S; L 101  is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal. 
     In one aspect, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another aspect, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc + /Fc couple less than about 0.6 V. 
     Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018. 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     c) EBL: 
     An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below. 
     d) Hosts: 
     The light emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied. 
     Examples of metal complexes used as host are preferred to have the following general formula: 
     
       
         
         
             
             
         
       
     
     wherein Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103  and Y 104  are independently selected from C, N, O, P, and S; L 101  is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal. 
     In one aspect, the metal complexes are: 
     
       
         
         
             
             
         
       
     
     wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N. 
     In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y 103 -Y 104 ) is a carbene ligand. 
     In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. 
     In one aspect, the host compound contains at least one of the following groups in the molecule: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein R 101  is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar&#39;s mentioned above. k is an integer from 0 to 20 or 1 to 20. X 101  to X 108  are independently selected from C (including CH) or N. Z 101  and Z 102  are independently selected from NR 101 , O, or S. 
     Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803, 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     e) Additional Emitters: 
     One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes. 
     Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450. 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     f) HBL: 
     A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface. 
     In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above. 
     In another aspect, compound used in HBL contains at least one of the following groups in the molecule: 
     
       
         
         
             
             
         
       
     
     wherein k is an integer from 1 to 20; L 101  is another ligand, k′ is an integer from 1 to 3. 
     g) ETL: 
     Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons. 
     In one aspect, compound used in ETL contains at least one of the following groups in the molecule: 
     
       
         
         
             
             
         
       
     
     wherein R 101  is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar&#39;s mentioned above. Ar 1  to Ar 3  has the similar definition as Ar&#39;s mentioned above. k is an integer from 1 to 20. X 101  to X 108  is selected from C (including CH) or N. 
     In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula: 
     
       
         
         
             
             
         
       
     
     wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L 101  is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal. 
     Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535, 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     h) Charge Generation Layer (CGL) 
     In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers. 
     In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen of the compound being deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof. 
     It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting. 
     Experimental Data 
     Synthesis of Comparison Compound 1 
     
       
         
         
             
             
         
       
     
     1.1 1-(4-(tert-Butyl)naphthalen-2-yl)-7-chlorobenzo[4,5]thieno[2,3-c]pyridine 
     
       
         
         
             
             
         
       
     
     A multi-necked flask, equipped with a thermocouple, mechanical stirrer and reflux condenser, was charged with 1,7-dichlorobenzo-[4,5]thieno[2,3-c]pyridine (75 g, 296 mmol, 1.005 equiv), 2-(4-(tert-butyl)naph-thalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (91.4 g, 295 mmol, 1.0 equiv), potassium carbonate (83 g, 590 mmol, 2.0 equiv), 1,4-dioxane (1500 mL) and water (300 mL). The suspension was sparged with nitrogen for 25 minutes then tetrakis(triphenylphosphine)palladium(0) (17 g, 14.7 mmol, 0.05 equiv) added. The reaction mixture was heated to reflux for 18 hours at which time LCMS analysis showed the reaction was complete. The reaction mixture was cooled to room temperature, the layers separated and the aqueous phase extracted with ethyl acetate (1×100 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was suspended in water (500 mL) and stirred for 1 hour. The suspension was filtered and the chunky solid triturated with acetonitrile (5 volumes) at 45° C. for 1 hour. The suspension was filtered while warm then the solid dried in a vacuum oven at 50° C. for 3 hours. The acetonitrile filtrate was concentrated to ˜½ volume and allowed to cool. The suspension was filtered and the solid washed with acetonitrile (2×50 mL). The solid was combined with the previous batch then dried continued in a vacuum oven at 50° C. overnight to give 1-(4-(tert-butyl)naphthalen-2-yl)-7-chlorobenzo[4,5]-thieno[2,3-c]pyridine (106 g, 88% yield, 98% purity) as an off-white solid. 
     1.2 1-(4-(tert-Butyl)naphthalen-2-yl)-7-neopentylbenzo[4,5]thieno[2,3-c]pyridine 
     
       
         
         
             
             
         
       
     
     A solution of 1-(4-(tert-butyl)naphthalen-2-yl)-7-chlorobenzo[4,5]-thieno[2,3-c]pyridine (106 g, 264 mmol, 1.0 equiv) in anhydrous tetrahydrofuran (1 L) was sparged with nitrogen for 10 minutes. Palladium(II) acetate (1.8 g, 7.9 mmol, 0.03 equiv) and 2-dicyclohexylphosphino-2′,6′-dimethoxy-biphenyl (SPhos) (6.5 g, 15.9 mmol, 0.06 equiv) were added and sparging continued for 5 minutes. The reaction mixture was heated to 35° C. and ˜0.48 M neopentylzinc-(II) bromide in tetrahydrofuran (600 mL, 288 mmol, 1.1 equiv) added dropwise keeping the temperature &lt;50° C. The reaction mixture was heated at 50° C. for 1 hour The reaction mixture was quenched with saturated aqueous sodium carbonate (500 mL). The mixture was filtered through Celite (200 g), the pad washed with ethyl acetate (3×100 mL) and the layers of the filtrate separated. The organic layer was washed with saturated brine (200 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure. The black oil was suspended in acetonitrile (500 mL) and stirred for 1 hour. The suspension was filtered to give 1-(4-(tert-butyl)naphthalen-2-yl)-7-neopentyl-benzo[4,5]thieno[2,3-c]pyridine (104 g) as a grey solid. 
     1.3 Di-μ-chloro-tetrakis[(1-(4-(tert-butyl)naphthalen-2-yl)-1′-yl)-7-neopentyl-benzo-[4,5]thieno[2,3-c]pyridin-2-yl]diiridium(III) 
     
       
         
         
             
             
         
       
     
     A solution of 1-(4-(tert-butyl)naphthalen-2-yl)-8-isobutylbenzo[4,5]thieno[2,3-c]pyridine (3.3 g, 7.53 mmol, 2.0 equiv) in 2-ethoxyethanol (132 mL) and DIUF water (33 mL) was sparged with nitrogen for 15 minutes. Iridium(III) chloride hydrate (1.39 g, 3.76 mmol, 1.0 equiv) was added then the reaction mixture heated at 98° C. After 24 hours,  1 H NMR analysis indicated the reaction was complete. The reaction mixture was cooled to 35° C., the suspension filtered and the solids washed with DIUF water (3×25 mL) and methanol (3×25 mL). The solid was dried in a vacuum oven at 40° C. for 2 hours to give di-μ-chloro-tetrakis-[(1-(4-(tert-butyl)naphthalen-2-yl)-1′-yl)-7-neopentylbenzo[4,5]thieno[2,3-c]pyridin-2-yl]-diiridium(III) (4.07 g, 98% yield) as a dark red solid. 
     1.4 Comparison Compound 1, Bis[1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-7-neopentyl benzo[4,5]thieno[2,3-c]pyridin-1-yl]-[3,7-diethyl-4,6-nonanedionato-k 2 O,O′]iridium(III)) 
     
       
         
         
             
             
         
       
     
     To a solution of di-μ-chloro-tetrakis-[(1-(4-(tert-butyl)naphthalen-2-yl)-1′-yl)-7-neopentylbenzo [4,5]thieno[2,3-c]pyridin-2-yl]-diiridium(III) (2.0 g, 0.9 mmol, 1.0 equiv) in 1:1 mixture of dichloromethane and methanol (30 mL) was added 3,7-diethylnonane-4,6-dione (483 mg, 2.18 mmol, 2.4 equiv) and the reaction mixture sparged with nitrogen for 5 minutes. Powdered potassium carbonate (376 mg, 2.72 mmol, 3.0 equiv) was added then the reaction mixture heated at 40° C. in a flask wrapped in foil to exclude light. After 26 hours,  1 H NMR analysis indicated the reaction was complete. The reaction mixture was cooled to room temperature, methanol (50 mL) added and the slurry stirred for 30 minutes. The suspension was filtered and the solid washed with methanol (3×10 mL). The residue (3.0 g) was dissolved in dichloromethane (100 mL) and dry-loaded onto basic alumina (30 g). The adsorbed material was purified on an Interchim automated chromatography system (80 g, silica gel cartridge), eluting with 0-50% dichloromethane in hexanes. The residue was triturated with methanol (50 mL) at 50° C. for 1 hour, filtered then dried in a vacuum oven at ˜40° C. for 2-3 hours to give bis[1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-7-neopentylbenzo[4,5]thieno[2,3-c]pyridin-1-yl]-[3,7-diethyl-4,6-nonanedionato-k 2 O,O′]iridium(III), Comparison Compound 1 as a red solid. 
     Synthesis of the Inventive Compound 1 
     
       
         
         
             
             
         
       
     
     2.1 (Trimethylsilyl)methylzinc(II) bromide 
     
       
         
         
             
             
         
       
     
     With continuous stirring, a mixture of zinc powder (19.56 g, 299 mmol, 2.0 equiv) and anhydrous lithium chloride (12.68 g, 299 mmol, 2.0 equiv) was heated at 100° C. (internal temperature) for 10 minutes under vacuum. After cooling to room temperature, 1,2-dibromoethane (1.405 g, 7.48 mmol, 0.05 equiv in anhydrous tetrahydrofuran (150 mL was added and the reaction mixture heated at reflux for 30 minutes. After cooling to ˜35° C., chlorotrimethyl silane (0.163 g, 1.496 mmol, 0.01 equiv) then (bromo-methyl)trimethylsilane (25 g, 150 mmol, 1.0 equiv were sequentially added. Iodine (0.190 g, 0.748 mmol, 0.005 equiv) was added then the reaction mixture heated at 65° C. overnight. The reaction mixture was cooled to room temperature, and the solids allowed to settle. The solution was decanted into a storage bottle. The solids were washed with anhydrous tetrahydrofuran (20 mL) and the wash added to the bottle to give a 0.80M solution of (trimethylsilyl)methylzinc(II) bromide (˜150 mL). 
     2.2 1-(4-(tert-Butyl)naphthalen-2-yl)-7-chlorobenzo[4,5]thieno[2,3-c]pyridine 
     
       
         
         
             
             
         
       
     
     A mixture of 1,7-dichlorobenzo[4,5]thieno[2,3-c]pyridine (20 g, 79 mmol, 1.0 equiv), 2-(4-(tert-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-di-oxaborolane (24.42 g, 79 mmol, 1.0 equiv), potassium carbonate (21.75 g, 157 mmol, 2.0 equiv), 1,4-dioxane (400 mL) and water (75 mL) was sparged with nitrogen for 15 minutes. tetrakis-(Triphenylphosphine)palladium(0) (4.55 g, 3.94 mmol, 0.05 equiv) was added, sparging continued for 10 minutes then the reaction mixture heated at reflux for 4 hours. The reaction mixture was cooled to room temperature and water (400 mL) added. The suspension was filtered, the solid washed with water (50 mL) then methanol (100 mL). The yellow solid (30 g, 93.4% LCMS purity) was triturated with acetonitrile (2×100 mL) at 55° C. for 0.5 hour to give 1-(4-(tert-butyl)naphthalen-2-yl)-7-chlorobenzo[4,5]thieno-[2,3-c]pyridine (22 g, 70% yield, 97.9% LCMS purity), containing bis-coupled by-product (0.7%), as a light yellow solid. 
     2.3 1-(4-(tert-Butyl)naphthalen-2-yl)-7-(trimethylsilyl)methylbenzo[4,5]thieno-[2,3-c]pyridine 
     
       
         
         
             
             
         
       
     
     A mixture of 1-(4-(tert-butyl)naphthalen-2-yl)-7-chlorobenzo[4,5]thieno[2,3-c]pyridine (5.0 g, 12.44 mmol, 1.0 equiv), 2-dicyclohexylphosphino-2′,6′-bis(N,N-dimethylamino) biphenyl (CPhos) (00.326 g, 0.746 mmol, 0.06 equiv) and palladium(II) acetate (0.084 g, 0.376 mmol, 0.03 equiv) in anhydrous tetrahydrofuran (65 mL) was cooled to −10° C. in a brine-ice bath. The mixture was sparged with nitrogen for 15 minutes. 0.8M (trimethylsilyl)methylzinc(II) bromide in tetrahydrofuran (23.32 mL, 18.66 mmol, 1.5 equiv) was added slowly then the reaction mixture stirred at room temperature overnight. The reaction mixture was directly loaded onto silica gel (100 g) in a dry-load cartridge and purified on a silica gel column, eluting with 5-40% ethyl acetate in hexanes. Product fractions were concentrated to give 1-(4-(tert-butyl)naphthalen-2-yl)-7-((trimethylsilyl)methyl) benzo[4,5]thieno-[2,3-c]pyridine (4.24 g, 75% yield, 99.9% purity) as an off-white solid. 
     2.4 Inventive Compound 1, Bis[(1-(4-(tert-butyl)naphthalen-2-yl)-1′-yl)-7-((trimethylsilyl)methyl)benzo [4,5]thieno[2,3-c]pyridin-2-yl]-(3,7-diethyl-4,6-nonanedionato-k 2 O,O′)-iridium(III) 
     
       
         
         
             
             
         
       
     
     A suspension of 1-(4-(tert-butyl)naph-thalen-2-yl)-7-((trimethylsilyl)methyl)benzo[4,5] thieno[2,3-c]pyridine (4.26 g, 4.69 mmol, 2.2 equiv) and iridium(III) chloride hydrate (1.35 g, 2.132 mmol, 1.0 equiv) in 2-ethoxyethanol (60 mL) and DIUF water (20 mL) was heated at 100° C. overnight. The reaction mixture was cooled to room temperature and diluted with DIUF water (200 mL). The red solid was filtered and washed with water (25 mL), then methanol (50 mL) to give crude μ-dichloride complex. 
     
       
         
         
             
             
         
       
     
     A mixture of μ-dichloride complex (3.79 g, 1.672 mmol, 1.0 equiv), 3,7-diethylnonane-4,6-dione (0.71 g, 3.34 mmol, 2.0 equiv) and powdered potassium carbonate (0.693 g, 5.02 mmol, 3.0 equiv) in dichloro-methane (50 mL) and methanol (50 mL) was heated at 40° C. for 16 h.  1 H NMR analysis indicated the μ-dichloride complex was consumed. The reaction mixture was cooled to room temperature, concentrated under reduced pressure and DIUF water (200 mL) added. The suspension was filtered and the solid washed with DIUF water (50 mL) then methanol (10 mL). 
     The red solid was dissolved in dichloromethane (100 mL) and adsorbed onto silica gel (100 g). The adsorbed material was purified on silica gel column, eluting with a gradient of 5-50% dichloromethane in hexanes. Product fractions were concen-trated under reduced pressure. The residue was triturated with methanol (50 mL) at room temperature to give compound Inventive Compound 1 (4.3 g, 83% yield, 85.0% purity) as red solid. 
     The material was repurified on silica gel column, eluting with a gradient of 5-50% dichloromethane in hexanes. Cleanest product fractions were concentrated under reduced pressure to give Inventive Compound 1, bis[(1-(4-(tert-butyl)naphthalen-2-yl)-1′-yl)-7-((trimethylsilyl)methyl)benzo[4,5]thieno[2,3-c]-pyridin-2-yl]-[3,7-diethyl-4,6-nonanedionato-k 2 O,O′]iridium(III) (1.7 g, 99.6% purity) as a red solid. 
     Synthesis of the Comparison Compound 2 
     
       
         
         
             
             
         
       
     
     3.1 1-(4-(tert-Butyl)naphthalen-2-yl)-7-chloro-8-methylbenzo[4,5]thieno[2,3-c]pyridine 
     
       
         
         
             
             
         
       
     
     A 5 L multi-necked flask, equipped with a thermocouple, mechanical stirrer and reflux condenser, was charged with 1,7-dichloro-8-methylbenzo[4,5]thieno[2,3-c]pyridine (250 g, 930 mmol, 1.0 equiv), 2-(4-(tert-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (290.0 g, 939 mmol, 1.01 equiv), 1,4-dioxane (2.5 L) and 2.0M aqueous potassium carbonate (930 mL, 1860 mmol, 2.0 equiv). The suspension was sparged with nitrogen for 25 minutes. trans-Dichlorobis(triphenylphosphine)-palladium(II) (19.7 g, 28.0 mmol, 0.03 equiv) was added then the reaction mixture heated at reflux for 18 hours. LCMS analysis indicated &gt;95% of starting material was consumed. The reaction mixture was cooled to room temperature and filtered. The solid was washed with water (3×500 mL) and methyl tert-butyl ether (3×200 mL). The solids from 3 reactions (total of 2.93 mol of starting material), were combined and dried in a vacuum oven at 50° C. for 16 hours to give 1-(4-(tert-butyl)naphthalen-2-yl)-7-chloro-8-methylbenzo[4,5] thieno[2,3-c]pyridine (1113 g, 78% yield, 86% Q-NMR purity) as a greenish-yellow solid. 
     3.2 1-(4-(tert-Butyl)naphthalen-2-yl)-8-methyl-7-neopentylbenzo[4,5]thieno[2,3-c]pyridine 
     
       
         
         
             
             
         
       
     
     A solution of 1-(4-(tert-butyl)naphthalen-2-yl)-7-chloro-8-methylbenzo[4,5]thieno[2,3-c]pyridine (10 g, 24.04 mmol, 1.0 equiv) in anhydrous tetrahydrofuran (100 mL) was sparged with nitrogen for 20 minutes. Palladium(II) acetate (162 mg, 0.72 mmol, 0.03 equiv) and 2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl (SPhos) (592 mg, 1.44 mmol, 0.06 equiv) were added then the reaction mixture warmed to 30° C. while sparging with nitrogen. ˜0.35M neo-pentylzinc(II) bromide solution in tetrahydrofuran (92 mL, 33.7 mmol, 1.4 equiv) was added slowly, keeping the reaction temperature below 50° C. The reaction mixture was heated at 50° C. for 16 hours, at which time the solution had darkened. The reaction mixture was cooled then quenched by addition of a 1:2 mixture of saturated aqueous sodium sulfite and saturated aqueous sodium carbonate (200 mL). The mixture was stirred for 30 minutes then filtered through a pad of Celite (50 g). The pad was washed with water (50 mL) and ethyl acetate (3×50 mL) and the layers of the filtrate separated. The organic layer was washed with saturated brine (2×20 mL). The aqueous layers were extracted with ethyl acetate (50 mL). The combined organic layers were dried over sodium sulfate, filtered through silica gel (10 g) and concentrated to give an foamy orange solid (12.1 g, &gt;100% yield). 
     3.3 Di-μ-chloro-tetrakis[1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-neopentylbenzo[4,5]thieno[2,3-c]pyridin-1-yl]diiridium(III) 
     
       
         
         
             
             
         
       
     
     A solution of 1-(4-(tert-butyl)naphthalen-2-yl)-8-methyl-7-neopentylbenzo[4,5]-thieno[2,3-c]pyridine (7.5 g, 16.6 mmol, 2.0 equiv) in 2-ethoxyethanol (120 mL) and DIUF water (30 mL) was sparged with nitrogen for 15 minutes. Iridium(III) chloride hydrate (3.1 g, 8.3 mmol, 1.0 equiv) was added then the reaction mixture heated at reflux for 36 hours.  1 H NMR analysis indicated the reaction was complete. The reaction mixture was cooled to 35° C., the suspension filtered and the solid washed with methanol (3×50 mL). Drying in a vacuum oven at 55° C. for 3 hours gave di-μ-chloro-tetrakis[(1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-neopentylbenzo[4,5]thieno[2,3-c]pyridin-2-yl]diiridium(III) (7.6 g, 81% yield) as a dark red solid. 
     Bis[(1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-neopentylbenzo-[4,5]-thieno[2,3-c]pyridin-2-yl]-[3,7-diethylnonane-4,6-dionato-k 2 O,O′]-iridium(III), Comparison Compound 2 
     
       
         
         
             
             
         
       
     
     To a nitrogen-sparged solution of di-μ-chloro-tetrakis [(1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-neopentyl-benzo[4,5]thieno [2,3-c]pyridin-2-yl]diiridium(III) (3.6 g, 1.6 mmol, 1.0 equiv) in a 1:1 mixture of dichloromethane and methanol (32 mL) was added 3,7-diethyl-nonane-4,6-dione (0.846 g, 4 mmol, 2.5 equiv). Powdered potassium carbonate (0.661 g, 4.8 mmol, 3.0 equiv) was added then the reaction mixture heated at 40° C. for 4 days in a flask wrapped in foil to exclude light.  1 H NMR analysis indicated the reaction was complete. The reaction mixture was poured into methanol (400 mL) and the suspension filtered. The red solid was washed with methanol (150 mL) and DIUF water (250 mL) then dried in a vacuum oven at 45° C. for 2 hours. The red solid (2.9 g) was adsorbed onto basic alumina (100 g) and loaded into a 100 g dry-load cartridge. The adsorbed material was purified on silica gel column, eluting with 15-35% dichloromethane in hexanes. Purest product fractions were concentrated under reduced pressure. The red solid was triturated with methanol (20 volumes) for ˜30 minutes, filtered and dried in a vacuum oven at 45° C. for 18 hours to give bis[(1-(4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-neopentyl-benzo[4,5]thieno-[2,3-c]pyridin-2-yl]-[3,7-diethylnonane-4,6-dionato-k 2 O,O′]-iridium(III), Comparison Compound 2 (1.6 g, 35% yield, 99.9% UPLC purity) as a red solid. 
     Synthesis of the Inventive Compound 2 
     
       
         
         
             
             
         
       
     
     4.1 1-(4-(tert-Butyl)naphthalen-2-yl)-7-chloro-8-methylbenzo[4,5]thieno[2,3-c] pyridine 
     
       
         
         
             
             
         
       
     
     A 5 L multi-necked flask, equipped with a thermocouple, mechanical stirrer and reflux condenser, was charged with 1,7-dichloro-8-methylbenzo[4,5]thieno[2,3-c]pyridine (250 g, 930 mmol, 1.0 equiv), 2-(4-(tert-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (290.0 g, 939 mmol, 1.01 equiv), 1,4-dioxane (2.5 L) and 2.0M aqueous potassium carbonate (930 mL, 1860 mmol, 2.0 equiv). The suspension was sparged with nitrogen for 25 minutes. Trans-dichlorobis(triphenylphosphine)-palladium(II) (19.7 g, 28.0 mmol, 0.03 equiv) was added then the reaction mixture heated at reflux for 18 hours. The reaction mixture was cooled to room temperature and filtered. The solid was washed with water (3×500 mL) and methyl tert-butyl ether (3×200 mL). The solids from 3 reactions, total of 2.93 mol of starting material, were combined and dried in a vacuum oven at 50° C. for 16 hours to give 1-(4-(tert-butyl)naphthalen-2-yl)-7-chloro-8-methylbenzo[4,5]thieno-[2,3-c]pyridine (1113 g, 78% yield) as a greenish-yellow solid. 
     4.2 1-(4-(tert-Butyl)naphthalen-2-yl)-8-methyl-7-((trimethylsilyl)methyl)benzo-[4,5]thieno[2,3-c]pyridine 
     
       
         
         
             
             
         
       
     
     To a nitrogen sparged solution of 1-(4-(tert-butyl)naphthalen-2-yl)-7-chloro-8-methylbenzo[4,5]thieno[2,3-c]pyridine (8.04 g, 19.3 mmol, 1.0 equiv) in anhydrous tetrahydrofuran (100 mL) were added 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos) (0.824 g, 2.0 mmol, 0.1 equiv) and palladium(II) acetate (0.220 g, 0.98 mmol, 0.05 equiv). The mixture was stirred for 10 minutes. 1.1 M ((trimethylsilyl)methyl)zinc bromide in tetrahydrofuran (30 mL, 33.0 mmol, 1.7 equiv) was added via syringe and the reaction mixture was left to stir at room temperature for 16 hours. LCMS analysis indicated the reaction was complete. The mixture was poured into water (1 L) and ethyl acetate (900 mL). The layers were separated and the aqueous layer extracted with ethyl acetate (2×500 mL). The combined organic layers were washed with saturate brine (2×350 mL), dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 1-(4-(tert-butyl) naphthalen-2-yl)-8-methyl-7-((trimethylsilyl) methyl)benzo-[4,5]thieno[2,3-c]pyridine (14.2 g, &gt;100% yield; still wet) as a tan solid. 
     4.3 Di-μ-chloro-tetrakis-[1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-((trimethylsilyl)methyl)benzo [4,5]thieno[2,3-c]pyridin-2-yl] diiridium(III) 
     
       
         
         
             
             
         
       
     
     To a nitrogen sparged solution of 1-(4-(tert-butyl)naphthalen-2-yl)-8-methyl-7-((trimethylsilyl)methyl) benzo-[4,5]thieno[2,3-c]pyridine (3.72 g, 7.95 mmol, 1.9 equiv) in a 3:1 mixture of 2-ethoxyethanol and DIUF water (150 mL) was added iridium(III) chloride hydrate (1.34 g, 4.23 mmol, 1.0 equiv) and the reaction mixture heated at 103° C. After 16 hours, the reaction mixture was cooled to room temperature, filtered, the solids washed with DIUF water (100 mL) and methanol (50 mL) to give di-μ-chloro-tetrakis-[1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-((trimethylsilyl)methyl)benzo[4,5]thieno [2,3-c]pyridin-2-yl]diiridium(III) (5.2 g, &gt;100% yield; still wet) as a red solid. 
     4.4 Bis[1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-((trimethylsilyl) methyl)benzo[4,5]thieno[2,3-c]pyridin-2-yl]-(3,7-diethylnonane-4,6-dionato-k 2 O,O′) iridium(III) 
     
       
         
         
             
             
         
       
     
     To a nitrogen sparged solution of di-μ-chloro-tetrakis-[1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7-((trimethyl silyl)methyl)benzo[4,5]thieno[2,3-c]pyridin-2-yl]diiridium(III) ((4.91 g, wet), est. 2.1 mmol, 1.0 equiv) in a 1:1 mixture of dichloromethane and methanol (150 mL) was added, via syringe, 3,7-diethylnonane-4,6-dione (2 g, 9.42 mmol, 4.5 equiv). Powdered potassium carbonate (2.1 g, 15.2 mmol, 7.2 equiv) was added and the reaction mixture heated at 40° C. in a flask wrapped in foil to exclude light. After 16 hours,  1 H NMR analysis indicated the reaction was complete. The reaction mixture was concentrated under reduced pressure. The resulting residue was purified on an Interchim automated chromatography system, eluting with 15-30% dichloromethane in hexanes. The purest product fractions were concentrated under reduced pressure, triturated with methanol (15 volumes), and collected by filtration to give red solid (2.1 g, 99.5% UPLC purity). Mixed fractions were combined and purified on an Interchim automated chromatography system, eluting with 25% dichloromethane in hexanes. The red solids were dried in the vacuum oven at 50° C. for 16 hours to give Inventive Compound 2, bis[1-((4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-methyl-7 ((trimethylsilyl)methyl)benzo[4,5]thieno[2,3-c]pyridin-2-yl]-(3,7-diethylnonane-4,6-dionato-k 2 O,O′) iridium(III) (1.1 g, 99.5% UPLC purity). 
     Synthesis of Comparison Compound 3 
     
       
         
         
             
             
         
       
     
     [Ir(bis(5-(2,2-dimethylpropyl)-2-(4-methylphenyl-2′-yl)pyridin-1-yl)(-1H)) 2 -(MeOH) 2 ] trifluoromethanesulfonate 
     
       
         
         
             
             
         
       
     
     A 1 L 4-neck flask was charged with 2-ethoxyethanol (200 mL) and DIUF water (67 mL) and the mixture sparged with nitrogen for 15 minutes. Iridium(III) chloride hydrate (8.16 g, 25.8 mmol, 1.0 equiv) and 5-(2,2-dimethylpropyl)-2-(4-methylphenyl)pyridine (13.6 g, 56.8 mmol, 2.2 equiv) were added then the reaction mixture heated at reflux for 48 hours. The cooled reaction mixture was filtered, the solid washed with methanol then air-dried to give di-μ-chloro-tetrakis[κ2(C2,N)-5-(2,2-dimethylpropyl)-2-(4-methyl-phenyl-2′-yl)pyridin-1-yl)]diiridium(III) (11.34 g, 62% yield) as a yellow solid. 
     A 1 L flask was charged with di-μ-chloro-tetrakis[κ2(C2,N)-5-(2,2-dimethylpropyl)-2-4-methylphenyl-2′-yl)-pyridin-1-yl)]diiridium(III) (11.25 g, ˜7.99 mmol, 1.0 equiv) in dichloromethane (280 mL). The flask was wrapped with aluminum foil to exclude light and a solution of silver trifluoromethanesulfonate (4.86 g, 18.9 mmol, 2.37 equiv) in methanol (50 mL) added. The reaction mixture was stirred at room temperature for 24 hours then filtered through a pad of silica gel (100 g) topped with Celite (30 g), rinsing thoroughly with dichloromethane. The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven to give [Ir(bis(5-(2,2-di-methylpropyl)-2-(4-methylphenyl-2′-yl)pyridin-1-yl)(-1H)) 2 (MeOH)) 2 ] trifluoro-methanesulfonate (11.59 g, 82% yield) as a yellow solid. 
     Synthesis of Bis[5-(2,2-dimethylpropyl)-2-(4-methylphen-2′-yl)-pyridin-1-yl]-[8-(4-(2,2-di-methylpropyl-1,1-d 2 )pyridin-2-yl)-2-(methyl-d 3 )benzofuro[2,3-b]pyridin-7′-yl]iridium(III) 
     
       
         
         
             
             
         
       
     
     A 20 mL scintillation vial, equipped with a stir bar, was charged with [Ir(5-(2,2-dimethylpropyl))-(4-methylphenyl-2-yl)-2′-yl)pyridin-1-yl)(-1H)) 2 (MeOH) 2 ] trifluoromethanesulfonate (4.0 g, 4.53 mmol, 1.0 equiv), 8-(4-(2,2-dimethylpropyl-1,1-d 2 )pyridin-2-yl)-2-(methyl-d 3 )benzofuro[2,3-b]pyridine (1.52 g, 4.53 mmol, 1.0 equiv) and ethanol (67 mL). The mixture was sparged with nitrogen for 7 minutes. 2,6-Lutidine (0.53 mL, 4.53 mmol, 1.0 equiv) was added then the reaction mixture heated at 75° C. overnight. LCMS analysis showed the reaction was complete. The cooled reaction mixture was filtered and the solid washed with a small amount of methanol (˜10 mL). LCMS analysis showed the filtrate contained a significant amount of product. The solid and filtrate were recombined and concentrated under reduced pressure. The residue was filtered through basic alumina (140 g), eluting with dichloromethane. The filtrate was adsorbed onto Celite® (5 g) and purified on a silica gel column, eluting with a mixture of 75/5/20 to 85/15/0 toluene, dichloro-methane and hexanes. Pure fractions were concentrated under reduced pressure to give Comparison Compound 3 (4.1 g, 90% yield, 99.7% purity) as a bright yellow solid. The solid was dissolved in dichloromethane (10 mL) and methanol (˜400 mL) added to give some precipitates. Methanol (500 mL) was added resulting in a solution. The solution was partially concentrated in a rotary evaporator until copious amounts of solid were observed. The solid was filtered and dried in a vacuum oven at 45° C. overnight to give bis[5-(2,2-dimethylpropyl))-2-(4-methylphen-2′-yl)-pyridin-1-yl]-[8-(4-(2,2-dimethylpropyl-1,1-d 2 )pyridin-2-yl)-(2-(methyl-d 3 )benzofuro[2,3-b]pyridin-7′-yl]-iridium(III) (3.1 g, 99.6% UPLC purity) as a yellow solid. 
     Synthesis of Inventive Compound 3 
     
       
         
         
             
             
         
       
     
     6.1 Synthesis of 2-(p-Tolyl)-5-((trimethylsilyl)methyl)pyridine 
     
       
         
         
             
             
         
       
     
     5-Chloro-2-(p-tolyl)pyridine 
     A mixture of 2,5-dichloropyridine (60 g, 0.42 mol, 1.0 equiv), p-tolylboronic acid (57 g, 0.42 mol, 1.0 equiv) and sodium carbonate (311.7 g, 2.94 mol, 7.0 equiv), toluene (425 mL), ethanol (213 mL) and water (425 mL) was sparged with nitrogen for 15 min. Tetrakis(triphenylphos-phine)palladium(0) (14.6 g, 12.6 mmol, 0.03 equiv) was added then the reaction mixture heated at 76° C. for 16 hours. The cooled reaction mixture was diluted with ethyl acetate (400 mL) and water (400 mL). The organic layer was washed with brine (300 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was chromatographed on silica gel (400 g), eluting with 0-8% ethyl acetate in heptanes, to give 5-chloro-2-(p-tolyl)pyridine (78.12 g, 95% yield) as a white solid. 
     ((Trimethylsilyl)methyl)zinc(II) bromide 
     A sparged suspension of anhydrous lithium chloride (13.0 g, 307 mmol, 2.0 equiv) and zinc powder (20.1 g, 307 mmol, 2.0 equiv) in anhydrous tetrahydrofuran (150 mL) was heated to reflux then cooled to 40° C. 1,2-Dibromoethane (0.8 mL, 9.2 mmol, 0.06 equiv) and chlorotrimethylsilane (0.3 mL, 2.4 mmol, 0.02 equiv) were added quickly in succession. The reaction mixture was cooled to 45° C. and a small crystal of iodine added. (Bromomethyl)-trimethylsilane (25.3 g, 151 mmol, 1.0 equiv) was added in a quick stream then the reaction mixture was heated at 55° C. for 24 hours. The reaction mixture was cooled, the solids allowed to settle then the solution decanted into a bottle. Iodine trituration showed the solution was 0.8M in ((trimethylsilyl)methyl)zinc(II) bromide (80% yield). 
     2-(p-Tolyl)-5-((trimethylsilyl)methyl)pyridine 
     To a nitrogen sparged solution of 5-chloro-2-(p-tolyl)pyridine (15.1 g, 74 mmol, 1.0 equiv) in anhydrous tetrahydrofuran (500 mL) was added 2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl (SPhos) (3.1 g, 7.5 mmol, 0.1 equiv) and palladium(II) acetate (0.81 g, 3.6 mmol, 0.05 equiv). The reaction mixture was sparged with nitrogen for 10 minutes. 0.8M ((trimethylsilyl)methyl)zinc(II) bromide in tetrahydrofuran (105 mL, 84 mmol, 1.1 equiv) was added via syringe. The reaction mixture was heated at 55° C. for 24 hours when LCMS analysis showed the reaction was complete. The reaction mixture was cooled to room temperature and poured into water (1 L) and ethyl acetate (1 L). The layers were separated and the aqueous layer extracted with ethyl acetate (2×500 mL). The combined organic layers were washed with saturated brine (2×500 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give crude 2-(p-tolyl)-5-((tri-methylsilyl)methyl)pyridine (23.5 g, &gt;100% yield) as a brown residue containing residual solvent. 
     [Ir((5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)pyridin-1-yl)(-1H)) 2 -(MeOH) 2 ] trifluoromethanesulfonate 
     
       
         
         
             
             
         
       
     
     Di-μ-chloro-tetrakis[k2(C2,N)-5-((trimethylsilyl)methyl)-2-(4-methyl)phenyl-2′-yl)pyridin-1-yl]diiridiium(III) 
     A 50 mL 2-neck flask, fitted with a stir bar, condenser, nitrogen inlet and thermocouple, was charged with 2-(p-tolyl)-5-((trimethylsilyl)methyl)pyridine (2.75 g, 108 mmol, 4.2 equiv) and chlorobis(cyclooctene)iridium(I)dimer (2.30 g, 2.57 mmol, 1.0 equiv). 1,2-Dichlorobenzene (32 mL) was added, the system sparged with nitrogen for 10 minutes then heated at 80° C. overnight. LCMS analysis indicated the reaction was complete. The cooled reaction mixture was diluted with methanol (500 mL) and concentrated under reduced pressure. The dilution and concentration process was repeated until a small volume containing some solids was obtained. The mixture was treated with a 1:2 mixture of methanol and hexanes (˜300 mL) and rotated at high speed in a rotary evaporator, under no vacuum, until a copious amount of solid precipitated. The solid was filtered to give di-μ-chloro-tetrakis[k2(C2,N)-5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)pyridin-1-yl]-diiridiium(III) (2.84 g, 86% yield) as an orange-yellow solid. 
     [Ir((5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)pyridin-1-yl)(-1H)) 2 -(MeOH) 2 ] trifluoromethanesulfonate 
     A 250 mL round bottom flask, equipped with a stir bar, was charged with di-μ-chloro-tetrakis-[k2(C2,N)-5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)pyridin-1-yl]diiridiium(III) (4.2 g, 2.85 mmol, 1.0 equiv) and a 3:1 mixture of dichloromethane and methanol (64 mL). The mixture was sparged with nitrogen for 10 minutes. Silver trifluoro-methanesulfonate (1.83 g, 7.13 mmol, 2.5 equiv) was added, the flask covered with foil to exclude light then the reaction mixture stirred at room temperature for 2.5 hours.  1 H NMR analysis showed the reaction was complete. The reaction mixture was filtered through a short pad of Celite® (˜1″) topped with silica gel (˜1″), eluting with dichloromethane. Product fractions were concentrated under reduced pressure. Methanol (500 mL) was added to the residue and the mixture reconcentrated to give [Ir((5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)-pyridin-1-yl)(-1H)) 2  (MeOH) 2 ] trifluoromethanesulfonate (5.3 g, 96% yield) as yellow solid. 
     Bis[5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)pyridin-1-yl]-[8-((4-(2,2-dimethylpropyl-1,1-d 2 ) pyridin-2-yl)-1-yl)-2-(methyl-d 3 )benzofuro[2,3-b]-pyridin-7′-yl]iridium(III) 
     
       
         
         
             
             
         
       
     
     Bis[5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)pyridin-1-yl]-[8-((4-(2,2-dimethylpropyl-1,1-d 2 )pyridin-2-yl)-1-yl)-2-(methyl-d 3 )benzofuro[2,3-b]-pyridin-7′-yl]iridium(III) 
     A 100 mL 3 neck round bottom flask, equipped with a stir bar, condenser and thermowell, was charged with [Ir(5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)pyridin-1-yl)(-1H)) 2 -(MeOH) 2 ]trifluoromethanesulfonate (3.37 g, 3.69 mmol, 1.0 equiv), 8-(4-(2,2-dimethylpropyl-1,1-d 2 )pyridin-2-yl)-2-(methyl-d 3 )benzofuro[2,3-b]pyridine (1.24 g, 3.69 mmol, 1o equiv) and ethanol (66 mL). The mixture was sparged with nitrogen for 5 minutes. 2,6-Lutidine (0.43 mL, 3.69 mmol, 1.0 equiv) was added then the reaction mixture heated at 80° C. overnight. LCMS analysis showed the reaction was complete. The reaction mixture was cooled to room temperature and filtered. The solid (3.3 g, 99.6% LCMS purity) was filtered through a pad of basic alumina (35 g) topped with silica gel (15 g), eluting with dichloromethane. Product fractions were concentrated under reduced pressure. The residue was dissolved in a minimum volume of dichloromethane and precipitated with excess methanol. The solid was filtered and dried in a vacuum oven at 50° C. for 3 hour to give Inventive Compound 3, bis[5-((trimethylsilyl)methyl)-2-((4-methyl)phenyl-2′-yl)pyridin-1-yl]-[8-((4-(2,2-dimethylpropyl-1,1-d 2 )pyridin-2-yl)-1-yl)-(2-(methyl-d 3 )benzofuro[2,3-b]pyridin-7′-yl)iridium(III) (2.76 g, 72% yield, 99.4% UPLC purity) as a yellow solid. 
     Device Example for Inventive Compound 1, Inventive Compound 1 and Comparison Compound 1, Comparison Compound 2 
     Example device was fabricated by high vacuum (&lt;10 −7  Torr) thermal evaporation. The anode electrode was 1,200 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of Liq (8-hydroxyquinoline lithium) followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (&lt;1 ppm of H 2 O and O 2 ) immediately after fabrication, and a moisture getter was incorporated inside the package. The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of LG101 (purchased from LG Chem) as the hole injection layer (HIL); 400 Å of HTM as a hole transporting layer (HTL); 50 Å of EBM as an electron blocking layer (EBL); 400 Å of an emissive layer (EML) containing RH as red host, 18% of SD as a stability dopant, and 3% of emitter; and 350 Å of Liq (8-hydroxyquinoline lithium) doped with 35% of ETM as the electron transporting layer (ETL). 
                     TABLE 1                  Device layer materials and thicknesses                                 Layer   Material   Thickness [Å]                                             Anode   ITO   1,200           HIL   LG-101   100           HTL   HTM   400           EBL   EBM   50           EML   RH:SD 18%:Emitter 3%   400           ETL   Liq: ETM 35%   350           EIL   Liq   10           Cathode   Al   1,000                        
The chemical structures of the device materials are shown below. Inventive devices 1 and 2 were fabricated with Inventive Compounds 1 and 2; Comparison Devices were fabricated with Comparison Compounds 1 and 2:
 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Upon fabrication, the device was tested to measure EL and JVL. For this purpose, the samples were energized by the 2 channel Keysight B2902A SMU at a current density of 10 mA/cm 2  and measured by the Photo Research PR735 Spectroradiometer. Radiance (W/str/cm 2 ) from 380 nm to 1080 nm, and total integrated photon count were collected. The devices were then placed under a large area silicon photodiode for the JVL sweep. The integrated photon count of the device at 10 mA/cm 2  is used to convert the photodiode current to photon count. The voltage was swept from 0 to a voltage equating to 200 mA/cm 2 . The EQE of the device was calculated using the total integrated photon count. All results are summarized in Table 2 and Table 3. LE and LT 95%  of Inventive examples 1 and 2 are reported as relative numbers normalized to the results of the Comparative examples 1 and 2. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Device Results 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                   
                 At 10 mA/cm 2   
                 At 80 mA/cm 2   
               
               
                   
                 1931 CIE 
                 λ max 
                 relative 
                 relative 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Device 
                 Emitter 
                 x 
                 y 
                 [nm] 
                 LE [cd/A] 
                 LT 95%   
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Device 1 
                 Inventive Example 1 
                 0.673 
                 0.326 
                 620 
                 1.07 
                 0.92 
               
               
                 Device 2 
                 Comparative Example 1 
                 0.674 
                 0.325 
                 623 
                 1.00 
                 1.00 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Device Results 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                   
                 At 10 mA/cm 2   
                 At 80 mA/cm 2   
               
               
                   
                 1931 CIE 
                 λ max 
                 relative 
                 relative 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Device 
                 Emitter 
                 x 
                 y 
                 [nm] 
                 LE [cd/A] 
                 LT 95%   
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Device 3 
                 Inventive Example 2 
                 0.663 
                 0.336 
                 618 
                 1.15 
                 0.83 
               
               
                 Device 4 
                 Comparative Example 2 
                 0.673 
                 0.326 
                 621 
                 1.00 
                 1.00 
               
               
                   
               
            
           
         
       
     
     Table 2 and Table 3 provide summaries of performance of electroluminescence devices of the materials. The inventive compound devices (device 1 device 3) show higher LE, more saturated color than the comparative examples (device 2 and device 4). The number is beyond any value that could be attributed to experimental error and the observed improvement is significant. Lifetimes of the inventive devices were slightly lower, than comparative devices, but still acceptable for commercial application. All results show the great potentials of the inventive compounds for applications in organic light emitting diodes (OLED). 
     Device Examples for Compound 3 and Comparison Compound 3 
     All example devices were fabricated by high vacuum (&lt;10 −7  Torr) thermal evaporation. The anode electrode was 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of Liq (8-hydroxyquinoline lithium) followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (&lt;1 ppm of H 2 O and O 2 ) immediately after fabrication with a moisture getter incorporated inside the package. The organic stack of the device examples consisted of sequentially, from the ITO Surface: 100 Å of HAT-CN as the hole injection layer (HIL); 400 Å of HTM as a hole transporting layer (HTL); emissive layer (EML) with thickness 400 Å. Emissive layer containing H-host (H1): E-host (H2) in 6:4 ratio and 12 weight % of green emitter. 350 Å of Liq (8-hydroxyquinoline lithium) doped with 35% of ETM as the ETL. Device structure is shown in the table 1. Table 4 shows the schematic device structure. The chemical structures of the device materials are shown below. 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Upon fabrication the devices have been measured EL, JVL and life tested at DC 10 mA/cm 2 . L T97 at 9,000 nits was calculated from 80 mA/cm2 LT data assuming acceleration factor 1.8. Device structure and performance are shown in the tables below. Inventive devices 3 was fabricated with Inventive Compound 3; Comparison Device 3 was fabricated with Comparison Compound 3. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Schematic device structure 
               
            
           
           
               
               
               
               
            
               
                   
                 Layer 
                 Material 
                 Thickness [Å] 
               
               
                   
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Anode 
                 ITO 
                 800 
               
               
                   
                 HIL 
                 HAT-CN 
                 100 
               
               
                   
                 HTL 
                 HTM 
                 400 
               
               
                   
                 EBL 
                 EBM 
                 50 
               
               
                   
                 Green EML 
                 H1:H2: example dopant 
                 400 
               
               
                   
                 ETL 
                 Liq: ETM 35% 
                 350 
               
               
                   
                 EIL 
                 Liq 
                 10 
               
               
                   
                 Cathode 
                 Al 
                 1,000 
               
               
                   
                   
               
            
           
         
       
     
     The device data shows that Inventive Example exhibited similar color, voltage, and efficiencies within the experimental errors with the comparative example. However, the inventive example unexpectedly shows significantly higher device lifetime with 43% increment when compared with the comparative compound in the exact same device structure. This is a very important property for OLED application. This increment number is beyond any value that could be attributed to experimental error and the observed improvement is significant.