Patent Description:
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.

<CIT> discloses isomer-mixture metal complex compositions that include a plurality of atropisomers which are closely akin to each other in physical property and energy level and organic EL elements using the same.

In one aspect, the present disclosure provides a compound, Ir(LA)m(LB)<NUM>-m, having a structure of Formula I,
<CHM>
In Formula I:.

In another aspect, the present disclosure provides a formulation comprising a compound of Formula I as described herein.

In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound of Formula I 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 I as described herein.

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.

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.

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)-Rs).

The term "ester" refers to a substituted oxycarbonyl (-O-C(O)-Rs or -C(O)-O-Rs) radical.

The term "ether" refers to an -ORs radical.

The terms "sulfanyl" or "thio-ether" are used interchangeably and refer to a -SRs radical.

The term "selenyl" refers to a-SeRs radical.

The term "sulfinyl" refers to a -S(O)-Rs radical.

The term "sulfonyl" refers to a -SO<NUM>-Rs radical.

The term "phosphino" refers to a -P(Rs)<NUM> radical, wherein each Rs can be same or different.

The term "silyl" refers to a -Si(Rs)<NUM> radical, wherein each Rs can be same or different.

The term "germyl" refers to a -Ge(Rs)<NUM> radical, wherein each Rs can be same or different.

The term "boryl" refers to a -B(Rs)<NUM> radical or its Lewis adduct -B(Rs)<NUM> radical, wherein Rs can be same or different.

In each of the above, Rs 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 Rs 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, <NUM>-methylethyl, butyl, <NUM>-methylpropyl, <NUM>-methylpropyl, pentyl, <NUM>-methylbutyl, <NUM>-methylbutyl, <NUM>-methylbutyl, <NUM>,<NUM>-dimethylpropyl, <NUM>,<NUM>-dimethylpropyl, <NUM>,<NUM>-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 <NUM> to <NUM> ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[<NUM>. <NUM>]heptyl, spiro[<NUM>]decyl, spiro[<NUM>]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 <NUM> to <NUM> 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 <NUM> or <NUM> 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, <NUM>,<NUM>-azaborine, <NUM>,<NUM>-azaborine, <NUM>,<NUM>-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, boryl, 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<NUM> represents mono-substitution, then one R<NUM> must be other than H (i.e., a substitution). Similarly, when R<NUM> represents di-substitution, then two of R<NUM> must be other than H. Similarly, when R<NUM> represents zero or no substitution, R<NUM>, 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, <CIT>, Patent Pub. No. <CIT>, and U. Application Pub. No. <CIT> describe the making of deuterium-substituted organometallic complexes. Further reference is made to <NPL> and <NPL>, which 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 <NUM>, <NUM>' positions in a biphenyl, or <NUM>, <NUM> position in a naphthalene, as long as they can form a stable fused ring system.

In some embodiments, each of R<NUM>, R<NUM>, R<NUM>, R<NUM>, RA, RB, RC, R1a, R2a, R3a, R4a, and R5a is independently hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein. In some embodiments, each of each of R<NUM>, R<NUM>, R<NUM>, R<NUM>, RA, RB, RC, R1a, R2a, R3a, R4a, and R5a is independently hydrogen or a substituent selected from the group consisting of the more preferred general substituents defined herein. In some embodiments, each of each of R<NUM>, R<NUM>, R<NUM>, R<NUM>, RA, RB, RC, R1a, R2a, R3a, R4a, and R5a is independently hydrogen or a substituent selected from the group consisting of the most preferred general substituents defined herein.

In some embodiments, no two RA are joined or fused to form a ring. In some embodiments, no two RC are joined or fused to form a ring.

In some embodiments, each moiety A and moiety C is independently a <NUM>-membered and/or <NUM>-membered carbocyclic or heterocyclic ring. In some embodiments, each moiety A and moiety C is independently benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole. In some embodiments, each moiety A and moiety C is independently benzene or pyridine.

In some embodiments, each moiety A and moiety C is independently a polycyclic fused ring system comprising a total of at least two <NUM>-membered and/or <NUM>-membered carbocyclic or heterocyclic rings. In some embodiments, each moiety A and moiety C is independently a polycyclic fused ring system comprising a total of at least three <NUM>-membered and/or <NUM>-membered carbocyclic or heterocyclic rings. In some embodiments, each moiety A and moiety C is independently a polycyclic fused ring system comprising a total of at least four <NUM>-membered and/or <NUM>-membered carbocyclic or heterocyclic rings. In some embodiments, each moiety A and moiety C is independently a polycyclic fused ring system comprising a total of at least one <NUM>-membered carbocyclic or heterocyclic ring and at least two <NUM>-membered carbocyclic or heterocyclic rings.

In some embodiments, each moiety A and moiety C independently comprises a first ring coordinated to Ir, wherein the first ring is a <NUM>-membered ring; a second ring fused to the first ring, wherein the second ring is a <NUM>-membered ring; and a third ring fused to the second ring, wherein the third ring is a <NUM>-membered ring.

In some embodiments, each moiety A and moiety C is independently selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, and fluorene.

In some embodiments, each moiety A and moiety C is independently an aza version of the fused rings as described above. In some such embodiments, each moiety A and moiety C independently contains exact one aza N atom. In some such embodiments, each moiety A and moiety C contains exact two aza N atoms, which can be in one ring, or in two different rings. In some such embodiments, the ring having aza N atom is at least separated by another two rings from the Ir atom. In some such embodiments, the ring having aza N atom is at least separated by another three rings from the Ir atom. In some such embodiments, each of the ortho position of the aza N atom is substituted.

In some embodiments, at least one RA is selected from the group consisting of the Preferred General Substituents defined herein. In some embodiments, at least one RA is on the last fused ring(s) away from the Ir atom. In some embodiments, at least one RC is selected from the group consisting of the Preferred General Substituents defined herein. In some embodiments, at least one RC is on the last fused ring(s) away from the Ir atom.

In some such embodiments, the N of the imidazole moiety not coordinated to Ir is substituted by aryl, aryl-substituted aryl, or alkyl-substituted aryl, which can be partially or fully deuterated. In some such embodiments, the substitution is on the one or both of the ortho positions of the carbon atom which is attached to the N of the imidazole moiety not coordinated to Ir.

In some embodiments, two RB are joined or fused to form a <NUM>-membered and/or <NUM>-membered carbocyclic or heterocyclic ring. In some embodiments, two RB are joined or fused to form a <NUM>-membered and/or <NUM>-membered aryl or heteroaryl ring. In some embodiments, two RB are joined or fused to form a benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole group, which is fused to moiety B, and can be further substituted or fused. In some embodiments, two RB are joined or fused to form a benzo ring fused to moiety B.

In some embodiments, R<NUM> is a <NUM>-membered heterocyclic ring. In some embodiments, R<NUM> is a <NUM>-membered heterocyclic ring. In some embodiments, R<NUM> is a <NUM>-membered heterocyclic ring. In some embodiments, R<NUM> is a <NUM>-membered heterocyclic ring. In some embodiments, exactly one of R<NUM>, R<NUM>, R<NUM>, and R<NUM> is a <NUM>-membered heterocyclic ring.

In some embodiments, R<NUM> has a structure of Formula II. In some embodiments, R<NUM> has a structure of Formula II. In some embodiments, R<NUM> has a structure of Formula II. In some embodiments, R<NUM> has a structure of Formula II. In some embodiments, exactly one of R<NUM>, R<NUM>, R<NUM>, and R<NUM> has a structure of Formula II. In some embodiments, more than one of R<NUM>, R<NUM>, R<NUM>, R<NUM> has a structure of Formula II or is a <NUM>-membered heterocyclic ring;.

In some embodiments, R1a is selected from the group consisting of cycloalkyl, alkyl, silyl, germyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof. In some embodiments, R1a comprises at least <NUM> carbon atoms. In some embodiments, R1a comprises at least <NUM> carbon atoms. In some embodiments, R1a comprises at least <NUM> carbon atoms.

In some embodiments, R2a is selected from the group consisting of cycloalkyl, alkyl, silyl, germyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof. In some embodiments, R2a comprises at least <NUM> carbon atoms. In some embodiments, R2a comprises at least <NUM> carbon atoms. In some embodiments, R2a comprises at least <NUM> carbon atoms.

In some embodiments, R3a is selected from the group consisting of cycloalkyl, alkyl, silyl, germyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof. In some embodiments, R3a comprises at least <NUM> carbon atoms. In some embodiments, R3a comprises at least <NUM> carbon atoms. In some embodiments, R3a comprises at least <NUM> carbon atoms.

In some embodiments, R4a is selected from the group consisting of cycloalkyl, alkyl, silyl, germyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof. In some embodiments, R4a comprises at least <NUM> carbon atoms. In some embodiments, R4a comprises at least <NUM> carbon atoms. In some embodiments, R4a comprises at least <NUM> carbon atoms.

In some embodiments, R5a is selected from the group consisting of cycloalkyl, alkyl, silyl, germyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof. In some embodiments, R5a comprises at least <NUM> carbon atoms. In some embodiments, R5a comprises at least <NUM> carbon atoms. In some embodiments, R5a comprises at least <NUM> carbon atoms.

In some embodiments, none of X<NUM> to X<NUM> are N.

In some embodiments, at least one of X<NUM> to X<NUM> is N.

In some embodiments, exactly one of X<NUM> to X<NUM> is N.

In some embodiments, R1a and R5a are hydrogen.

In some embodiments, at least two of R1a to R5a are selected from the group consisting of cycloalkyl, alkyl, silyl, germyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.

In some embodiments, R<NUM> has a structure of Formula II and R3a is selected from the group consisting of cycloalkyl, alkyl, silyl, and germyl.

In some embodiments, RB is selected from the group consisting of aryl, alkyl, and combinations thereof. In some embodiments, RB is selected from the group consisting of <NUM>,<NUM>-diarylphenyl and <NUM>,<NUM>-dialkylphenyl.

In some embodiments, at least one of R1a, R2a, R3a, R4a, and R5a is independently hydrogen or a substituent selected from the group consisting of the structures of the following LIST <NUM>:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

In some embodiments, at least two of R1a, R2a, R3a, R4a, and R5a are independently selected from the group consisting of the structures of LIST <NUM>.

In some embodiments, moiety C is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, and fluorene.

In some embodiments, ligand LA is selected from the group consisting of:
<CHM>
and
<CHM>
where ring B1 is a <NUM>-membered or <NUM>-memerbed aryl or heteroaryl group;.

In some embodiments, B1 is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole. In some embodiments, RB2 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, their partially or fully deuterated or partially or fully fluorinated counterparts, and combinations thereof.

In some embodiments, the ligand LA is selected from the group consisting of
<CHM>
and
<CHM>
where ring B1 is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole; and RB2 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, their partially or fully deuterated or partially or fully fluorinated counterparts, and combinations thereof.

In some embodiments, the ligand LA is selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and
<CHM>
wherein X<NUM>, X<NUM>, X<NUM>, X<NUM>, X<NUM>, X<NUM> X<NUM>, X<NUM>, X<NUM>, and X<NUM> are each independently C or N; Y<NUM> for each occurrence is independently selected from the group consisting of BR, NR, PR, O, S, Se, C=O, S=O, SO<NUM>, CRR', SiRR', and GeRR'; ring B1 is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole; and RB2 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, their partially or fully deuterated or partially or fully fluorinated counterparts, and combinations thereof; RC1 represents mono to the maximum allowable substitution, or no substitution; each RC1 is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein;
R, and R' are each independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein; and two adjacent RB, RB1, or RC1 can be joined to form a ring.

In some embodiments, ligand LA is LAi, wherein i is an integer from <NUM> to <NUM>, and LA1 to LA100 have the structures in the following LIST <NUM>:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

In some embodiments, ligand LB is selected from the group consisting of
<CHM>
and
<CHM>
where:.

In some embodiments, two adjacent R<NUM>', R<NUM>', R<NUM>', R<NUM>', R2b or R3b are joined to form a fused <NUM>- or <NUM>-membered aromatic ring. In some embodiments, two adjacent R<NUM>', R<NUM>', R<NUM>', R<NUM>', R2b or R3b are joined to form a fused ring selected from the group consisting of selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, and fluorene.

In some embodiments, the ligand LB is selected from the group consisting of
<CHM>
<CHM>
where:.

In some embodiments, the ligand LB is LBn, wherein n is an integer from <NUM> to <NUM>, and each of LB1 to LB151 is defined in the following LIST <NUM>:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

In some embodiments, the compound has Formula Ir(LAi)(LBn)<NUM>, or Formula Ir(LAi)<NUM>(LBn), wherein i is an integer from <NUM> to <NUM>, and n is an integer from <NUM> to <NUM>, and the structures of LA1 to LA100 are defined in LIST <NUM> as defined herein, and structures of LB1 to LB151 are defined in LIST <NUM> as defined herein.

In some embodiments, the compound is at least <NUM>% deuterated. In some embodiments, the compound is at least <NUM>% deuterated. In some embodiments, the compound is at least <NUM>% deuterated. In some embodiments, the compound is at least <NUM>% deuterated. In some embodiments, the compound is at least <NUM>% deuterated. In some embodiments, the compound is at least <NUM>% deuterated. In some embodiments, the compound is at least <NUM>% deuterated. In some embodiments, the compound is fully deuterated.

In some embodiments, the compound is selected from the group consisting of the structures of the following LIST <NUM>:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

In some embodiments, the compound having the structure of Formula I described herein can be at least <NUM>% deuterated, at least <NUM>% deuterated, at least <NUM>% deuterated, at least <NUM>% deuterated, at least <NUM>% deuterated, at least <NUM>% deuterated, at least <NUM>% deuterated, at least <NUM>% deuterated, at least <NUM>% deuterated, or <NUM>% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percent of possible hydrogen atoms (e.g., positions that are hydrogen, deuterium, or halogen) that are replaced by deuterium atoms.

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 first organic layer may comprise a compound of Formula I defined 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 CnH2n+<NUM>, OCnH2n+<NUM>, OAr<NUM>, N(CnH2n+<NUM>)<NUM>, N(Ar<NUM>)(Ar<NUM>), CH=CH-CnH2n+<NUM>, C≡CCnH2n+<NUM>, Ar<NUM>, Ar<NUM>-Ar<NUM>, CnH2n-Ar<NUM>, or no substitution, wherein n is from <NUM> to <NUM>; and wherein Ar<NUM> and Ar<NUM> 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, 5λ2-benzo[d]benzo[<NUM>,<NUM>]imidazo[<NUM>,<NUM>-a]imidazole, <NUM>,<NUM>-dioxa-13b-boranaphtho[<NUM>,<NUM>,<NUM>-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[<NUM>,<NUM>]imidazo[<NUM>,<NUM>-a]imidazole, and aza-(<NUM>,<NUM>-dioxa-13b-boranaphtho[<NUM>,<NUM>,<NUM>-de]anthracene).

In some embodiments, the host may be selected from the HOST Group consisting of:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
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 emissive layer can comprise two hosts, a first host and a second host. In some embodiments, the first host is a hole transporting host, and the second host is an electron transporting host. In some embodiments, the first host and the second host can form an exciplex.

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 may comprise a compound of Formula I defined 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 pluraility 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 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 of Formula I defined 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 <NUM> inches diagonal, a <NUM>-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.

Several OLED materials and configurations are described in <CIT>,<CIT>, and <CIT>.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in <CIT>. An example of a p-doped hole transport layer is m-MTDATA doped with F<NUM>-TCNQ at a molar ratio of <NUM>:<NUM>, as disclosed in <CIT>. Examples of emissive and host materials are disclosed in <CIT>. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of <NUM>:<NUM>, as disclosed in <CIT>. <CIT> and <CIT> 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 <CIT> and <CIT>. Examples of injection layers are provided in <CIT>. A description of protective layers may be found in <CIT>.

The simple layered structure illustrated in <FIG> and <FIG> 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 <NUM>, hole transport layer <NUM> transports holes and injects holes into emissive layer <NUM>, 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 <FIG> and <FIG>.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in <CIT>. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in <CIT> The OLED structure may deviate from the simple layered structure illustrated in <FIG> and <FIG>. For example, the substrate may include an angled reflective surface to improve outcoupling, such as a mesa structure as described in <CIT>, and/or a pit structure as described in <CIT>.

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 <CIT> and <CIT>, organic vapor phase deposition (OVPD), such as described in <CIT>, and deposition by organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)), such as described in <CIT>. 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 <CIT> and <CIT> 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 <NUM> carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having <NUM> carbons or more may be used, and <NUM>-<NUM> 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 <CIT>, PCT Pat. Application Nos. <CIT> and <CIT>. 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 <NUM>:<NUM> to <NUM>:<NUM>. 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 <NUM> inches diagonal), <NUM>-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 <NUM> degrees C. to <NUM> degrees C. , and more preferably at room temperature (<NUM>-<NUM>), but could be used outside this temperature range, for example, from -<NUM> degree C to + <NUM>.

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 <NUM> inch diagonal or <NUM> square inch area. In some embodiments, the OLED is a display panel having at least <NUM> inch diagonal or <NUM> square inch area (wherein <NUM> square inch = <NUM><NUM>). 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.,<CIT>), 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 <NUM>% to <NUM>%. 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.

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.

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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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 MoOx; a p-type semiconducting organic compound, such as <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-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:
<CHM>.

Each of Ar<NUM> to Ar<NUM> 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 <NUM> to <NUM> 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<NUM> to Ar<NUM> is independently selected from the group consisting of:
<CHM>
<CHM>
wherein k is an integer from <NUM> to <NUM>; X<NUM> to X<NUM> is C (including CH) or N; Z<NUM> is NAr<NUM>, O, or S; Ar<NUM> 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:
<CHM>
wherein Met is a metal, which can have an atomic weight greater than <NUM>; (Y<NUM>-Y<NUM>) is a bidentate ligand, Y<NUM> and Y<NUM> are independently selected from C, N, O, P, and S; L<NUM> is an ancillary ligand; k' is an integer value from <NUM> 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<NUM>-Y<NUM>) is a <NUM>-phenylpyridine derivative. In another aspect, (Y<NUM>-Y<NUM>) 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 <NUM> 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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and
<CHM>.

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.

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:
<CHM>
wherein Met is a metal; (Y<NUM>-Y<NUM>) is a bidentate ligand, Y<NUM> and Y<NUM> are independently selected from C, N, O, P, and S; L<NUM> is an another ligand; k' is an integer value from <NUM> 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:
<CHM>
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<NUM>-Y<NUM>) 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 <NUM> to <NUM> 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:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
wherein R<NUM> 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's mentioned above. k is an integer from <NUM> to <NUM> or <NUM> to <NUM>. X<NUM> to X<NUM> are independently selected from C (including CH) or N. Z<NUM> and Z<NUM> are independently selected from NR<NUM>, 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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>,
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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:
<CHM>
wherein k is an integer from <NUM> to <NUM>; L<NUM> is another ligand, k' is an integer from <NUM> to <NUM>.

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:
<CHM>
<CHM>
wherein R<NUM> 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's mentioned above. Ar<NUM> to Ar<NUM> has the similar definition as Ar's mentioned above. k is an integer from <NUM> to <NUM>. X<NUM> to X<NUM> 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:
<CHM>
wherein (O-N) or (N-N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L<NUM> is another ligand; k' is an integer value from <NUM> 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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>,
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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 <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, and <NUM>%. 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.

A mixture of <NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl)-<NUM>H-benzo[d]imidazole (<NUM>, <NUM> mmol, <NUM> equiv) and iridium(III) chloride hydrate (<NUM>, <NUM> mmol, <NUM> equiv) in <NUM>-ethoxyethanol (<NUM>) and DIUF water (<NUM>) was heated at <NUM> for <NUM> hours. The cooled reaction mixture was filtered, the solid washed with methanol (<NUM> × <NUM>) then dried in a vacuum oven for a few hours at ~<NUM> to give di-µ-chloro-tetrakis[k2(C2,N)-<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>-benzo[d]imidazol-<NUM>-yl]diiridium (III) (<NUM>, <NUM>% yield) as a yellow solid.

A solution of silver trifluoromethanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv) in methanol (<NUM>) was added in one portion to a solution of di-µ-chloro-tetra-kis[k2(C2,N)-<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>-benzo[d]imidazol-<NUM>-yl]diiridium (III) (<NUM>, <NUM> mmol, <NUM> equiv) in dichloro-methane (<NUM>) and the flask wrapped with foil to exclude light. The reaction mixture was stirred at room temperature overnight under nitrogen. The reaction mixture was filtered through a short pad (~<NUM> inch (wherein <NUM> inch = <NUM>)) of silica gel, rinsing with dichloromethane (<NUM> × <NUM>) then a <NUM>:<NUM> mixture of dichloromethane and methanol (<NUM> × <NUM>). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at <NUM> overnight to give [Ir(<NUM>-(<NUM>,<NUM>-bis-(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>-benzo[d]imidazol-<NUM>-yl)-(<NUM>)<NUM>(MeOH)<NUM>] trifluoromethanesulfonate (<NUM>, <NUM>% yield) as a yellow-greenish solid.

A mixture of [Ir(<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>-benzo[d]imidazol-<NUM>-yl)(<NUM>)<NUM>(MeOH)<NUM>] trifluoromethanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv) and <NUM>-(dibenzo[b,d]furan-<NUM>-yl)-<NUM>-(<NUM>-(<NUM>,<NUM>-dimethyl-propyl-<NUM>,<NUM>-d<NUM>)phenyl)pyridine (<NUM>, <NUM> mmol, <NUM> equiv) in ethanol (<NUM>) was heated at <NUM> for <NUM> hours then <NUM>,<NUM>-lutidine (<NUM>, <NUM> mmol, <NUM> equiv) added. The reaction mixture was heated at <NUM> for <NUM> hours, cooled to room temperature then concentrated under reduced pressure. The residue was dissolved in toluene (~<NUM>) then loaded on to a Biotage automated chromatography system (<NUM> stacked <NUM> and one <NUM> silica gel cartridges), eluting with a gradient of <NUM>-<NUM>% toluene in hexanes. The recovered product (<NUM>, <NUM>% yield) was filtered through basic alumina (<NUM>), eluting with <NUM>% dichloromethane in hexanes. The recovered solid (<NUM>) was dissolved in dichloromethane (<NUM>) then precipitated with methanol (<NUM>) to give bis[<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>-benzo[d]imid-azol-<NUM>-yl]-[(<NUM>-(dibenzo[b,d]furan-<NUM>-yl)-<NUM>'-yl)-<NUM>-(<NUM>-(<NUM>,<NUM>-dimethylpropyl-<NUM>,<NUM>-d<NUM>)-phenyl)pyridin-<NUM>-yl)iridium(III) (<NUM>, <NUM>% UPLC purity) as a red-orange solid.

A mixture of <NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl)-<NUM>H-benzo-[d]imidazole (<NUM>, <NUM> mmol, <NUM> equiv) and iridium(III) chloride hydrate (<NUM>, <NUM> mmol, <NUM> equiv) in <NUM>-ethoxyethanol (<NUM>) and water (<NUM>) was heated at <NUM> for <NUM> hours. The cooled reaction mixture was filtered, the solid washed with methanol (<NUM> × <NUM>) then dried in a vacuum oven for a few hours at ~<NUM> to give di-µ-chloro-tetrakis[k2(C2,N)-<NUM>-(<NUM>,<NUM>-bis-(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>H-benzo[d]imid-azol-<NUM>-yl]-diiridium (III) (<NUM>, <NUM>% yield) as a yellow solid.

A solution of silver trifluoromethanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv) in methanol (<NUM>) was added in one portion to a solution of di-µ-chloro-tetrakis-[k2(C2,N)-<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>H-benzo[d]imidazol-<NUM>-yl]diiridium (III) (<NUM>, <NUM> mmol, <NUM> equiv) in dichloro-methane (<NUM>) and the flask wrapped with foil to exclude light. The reaction mixture was stirred at room temperature overnight under nitrogen. The reaction mixture was filtered through a short (~<NUM> inch (wherein <NUM> inch = <NUM>)) pad of silica gel, rinsing with dichloromethane (<NUM> × <NUM>) then a <NUM>:<NUM> mixture of dichloromethane and methanol (<NUM> × <NUM>). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at <NUM> overnight to give [Ir(<NUM>-(<NUM>,<NUM>-bis-(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>H-benzo[d]imidazol-<NUM>-yl)-(<NUM>H)<NUM>(MeOH)<NUM>] trifluoromethanesulfonate (<NUM>, <NUM>% yield) as a yellow-green solid.

A mixture of [Ir(<NUM>-(<NUM>,<NUM>-bis-(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>H-benzo[d]imidazol-<NUM>-yl)-(<NUM>H)<NUM>-[MeOH)<NUM>] trifluoromethanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv), <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylpropyl-<NUM>,<NUM>-d<NUM>)phenyl)-<NUM>-phenylpyridine (<NUM>, <NUM> mmol, <NUM> equiv) and <NUM>,<NUM>-lutidine (<NUM>, <NUM> mmol, <NUM> equiv) in ethanol (<NUM>) was heated at <NUM> for <NUM> hours. The cooled reaction mixture was concentrated under reduced pressure. The residue was purified on a Buchi automated chromatography system (<NUM> and <NUM> stacked silica gel cartridges), eluting with a gradient of <NUM>-<NUM>-<NUM>% dichloromethane in hexanes. The recovered product (<NUM>, <NUM>% UPLC purity) was re-purified on a Büchi automated chromatography system (<NUM> stacked <NUM> silica gel cartridges), eluting with a gradient of <NUM>-<NUM>-<NUM>% dichloromethane in hexanes. The recovered product (<NUM>) was filtered through basic alumina (<NUM>), eluting with <NUM>% dichloromethane in hexanes. The recovered solid (<NUM>) was dissolved in dichloromethane (<NUM>) and precipitated with methanol (<NUM>). The solid was filtered and dried in a vacuum oven at ~<NUM> overnight to give bis[<NUM>-(<NUM>,<NUM>-bis(pro-pan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>H-benzo[d]imidazol-<NUM>-yl][<NUM>-(<NUM>-(<NUM>,<NUM>-dimethylpropyl-<NUM>,<NUM>-d<NUM>)phenyl)-<NUM>-(phenyl-<NUM>'-yl)pyridin-<NUM>-yl]iridium(III) (<NUM>, <NUM>% yield, <NUM>% UPLC purity) as a red-orange solid.

A mixture of <NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl)-<NUM>H-benzo-[d]imidazole (<NUM>, <NUM> mmol, <NUM> equiv) and iridium(III) chloride hydrate (<NUM>, <NUM> mmol, <NUM> equiv), <NUM>-ethoxyethanol (<NUM>) and water (<NUM>) was heated at <NUM> for <NUM> hours. The cooled reaction mixture was filtered, the solid washed with methanol (<NUM> × <NUM>) then dried in a vacuum oven for a few hours at ~<NUM> to give di-µ-chloro-tetrakis[k2(C2,N)-<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>H-benzo[d]imid-azol-<NUM>-yl]diiridium (III) (<NUM>, <NUM>% yield) as a yellow solid.

A solution of silver trifluoromethanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv) in methanol (<NUM>) was added in one portion to a solution of di-µ-chloro-tetrakis-[k2(C2,N)-<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>H-benzo[d]imidazol-<NUM>-yl]diiridium (III) (<NUM>, <NUM> mmol, <NUM> equiv) in dichloro-methane (<NUM>) and the flask wrapped with foil to exclude light. The reaction mixture was stirred at room temperature overnight under nitrogen. The reaction mixture was filtered through a ~<NUM> inch (wherein <NUM> inch = <NUM>) pad of silica gel,
rinsing with dichloro-methane (<NUM> × <NUM>) then a <NUM>:<NUM> mixture of dichloromethane and methanol (<NUM> × <NUM>). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven at <NUM> overnight to give [Ir(<NUM>-(<NUM>,<NUM>-bis-(propan-<NUM>-yl-d<NUM>)-phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>H-benzo[d]imidazol-<NUM>-yl)-(<NUM>)<NUM>(MeOH)<NUM>] trifluoromethanesulfonate (<NUM>, <NUM>% yield) as a yellow-greenish solid.

A <NUM> <NUM>-neck flask was charged with Ir(<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>-benzo[d]imidazol-<NUM>-yl)(<NUM>)<NUM>(MeOH)<NUM>] trifluoro-methane sulfonate (<NUM>, <NUM> mmol, <NUM> equiv), <NUM>-(<NUM>-(<NUM>,<NUM>-di-methylpropyl-<NUM>,<NUM>-d<NUM>)phenyl-<NUM>,<NUM>-d<NUM>)-<NUM>-(naphtho[<NUM>,<NUM>-b]benzofuran-<NUM>-yl)pyridine (<NUM>, <NUM> mmol, <NUM> equiv) and ethanol (<NUM>). <NUM>,<NUM>-Lutidine (<NUM>, <NUM> mmol, <NUM> equiv) was added then the reaction mixture heated at <NUM>. After <NUM> hours, the reaction was determined complete by UPLC analysis, with <NUM>% conversion. The cooled reaction mixture was filtered and the solid washed with methanol (<NUM>). The crude material was purified on a Biotage automated chromatography system (<NUM> stacked <NUM> Biotage silica gel cartridges), eluting with <NUM>-<NUM>% tetrahydrofuran in hexanes. Pure fractions were concentrated under reduced pressure. The recovered product was dissolved in dichloromethane (<NUM>), precipitated with methanol (<NUM>) and the red-orange solids filtered. The recovered material (<NUM>% UPLC purity) was re-purified on a Biotage automated chromatography system (<NUM> stacked <NUM> Biotage silica gel cartridges), eluting with <NUM>-<NUM>% toluene in hexanes. Pure fractions were concentrated to an orange solid which was precipitated from dichloromethane (<NUM>) with methanol (<NUM>). The solid was filtered and dried in a vacuum oven overnight at <NUM> to give bis[<NUM>-(<NUM>,<NUM>-bis(propan-<NUM>-yl-d<NUM>)phenyl)-<NUM>-(<NUM>-(methyl-d<NUM>)phen-<NUM>'-yl)-<NUM>H-benzo-[d]imidazol-<NUM>-yl] [<NUM>-(<NUM>-(<NUM>,<NUM>-dimethylpropyl-<NUM>,<NUM>-d<NUM>)phenyl)-<NUM>-((naphtho[<NUM>,<NUM>-b]benzofuran-<NUM>-yl)-<NUM>'-yl)pyridin-<NUM>-yl]iridium(III) (<NUM>, <NUM>% yield, <NUM>% UPLC purity) as an orange solid.

To a solution of di-µ-chloro-tetrakis [κ2(C2,N)-<NUM>,<NUM>-bis(methyl-d<NUM>)-<NUM>-(<NUM>-(methyl-d<NUM>)-phenyl)pyridine]diiridium(III) (<NUM> <NUM> mmol, <NUM> equiv) in dichloromethane (<NUM>), in a flask wrapped with foil to exclude light, was added a solution of silver trifluoromethanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv) in methanol (<NUM>). The reaction mixture was stirred overnight at room temperature under nitrogen. The reaction mixture was filtered through a pad of silica gel pad (<NUM>) topped with Celite® (<NUM>), rinsing with dichloromethane (<NUM>). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven to give [Ir(<NUM>,<NUM>-bis(methyl-d<NUM>)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl)pyridine(-<NUM>))<NUM>(MeOH)<NUM>] trifluoromethanesulfonate (~<NUM>, <NUM>% yield) as a yellow solid.

A nitrogen flushed <NUM> <NUM>-neck flask was charged with [Ir(<NUM>,<NUM>-bis(methyl-d<NUM>)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl)-pyridine(-H))<NUM>(MeOH)<NUM>](trifluoromethanesulfonate) (<NUM>, <NUM> mmol, <NUM> equiv) and <NUM>-(dibenzo[b,d]furan-<NUM>-yl)-<NUM>-(<NUM>-(<NUM>,<NUM>-dimethylpropyl-<NUM>,<NUM>-d<NUM>)phenyl)-pyridine (<NUM>, <NUM> mmol, <NUM> equiv) and acetone (<NUM>). The mixture was sparged with nitrogen for <NUM> minutes and the flask wrapped in foil to exclude light. Triethylamine (<NUM>, <NUM> mmol, <NUM> equiv) was added then the reaction mixture was heated at <NUM> overnight. After <NUM> hours, the reaction mixture was cooled to room temperature, filtered through a pad of Celite® (<NUM>) and the filtrate was concentrated under reduced pressure. The residue was triturated with <NUM>% dichloromethane in methanol (<NUM>). The solid was filtered and washed with methanol (<NUM>) to give mer-complex (<NUM>, <NUM>% HPLC purity, <NUM>% Q NMR purity) as an orange solid.

The meridonal isomer was converted to the facial isomer via photoisomerization.

Crude product after photo reaction (~<NUM>) was filtered through a <NUM> inch pad of silica gel (~<NUM>) topped with a <NUM> inch (wherein <NUM> inch = <NUM>) pad of basic alumina (~<NUM>), eluting with <NUM>% dichloromethane in hexanes (<NUM>). Product fractions were concentrated under reduced pressure. The residue was dissolved in dichloromethane, adsorbed onto Celite® (<NUM>) and purified on a Biotage Isolera automated chromatography system (<NUM> stacked <NUM> Biotage HC silica gel cartridges), eluting with <NUM>-<NUM>% tetrahydrofuran in hexanes. Pure product fractions were concentrated under reduced pressure. The residue was dissolved dichloromethane (<NUM>) and precipitated with methanol (<NUM>). The solid was filtered and washed with methanol (<NUM>) to give bis[<NUM>-(<NUM>-(methyl-d<NUM>)phenyl-<NUM>'-yl)-<NUM>,<NUM>-bis(methyl-d<NUM>)-pyridin-<NUM>-yl][<NUM>-((dibenzo[b, d]furan-<NUM>-yl)-<NUM>'-yl)-<NUM>-(<NUM>-(<NUM>,<NUM>-di-methylpropyl-<NUM>,<NUM>-d<NUM>)-phenyl)pyridin-<NUM>-yl]iridium(III) (<NUM>, <NUM>% yield, <NUM>% UPLC purity) as a bright yellow solid.

To a solution of di-µ-chloro-tetrakis [κ2(C2,N)-<NUM>,<NUM>-bis(methyl-d<NUM>)-<NUM>-(<NUM>-(methyl-d<NUM>)-phenyl)pyridine]diiridium(III) (<NUM> <NUM> mmol, <NUM> equiv) in dichloromethane (<NUM>) was added a solution of silver trifluoromethanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv) in methanol (<NUM>) added. The flask was wrapped with foil to exclude light then the reaction mixture was stirred overnight at room temperature under nitrogen. The reaction mixture was filtered through a pad of silica gel (<NUM>) topped with Celite® (<NUM>), rinsing with dichloromethane (<NUM>). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven to give [Ir(<NUM>,<NUM>-bis(methyl-d<NUM>)-<NUM>-(<NUM>-(methyl-d<NUM>)phenyl)pyridine(-<NUM>))<NUM>-(MeOH)<NUM>] trifluoromethanesulfonate (~<NUM>, <NUM>% yield) as a yellow solid.

A <NUM>, <NUM>-neck flask was charged with [Ir(<NUM>,<NUM>-bis(methyl-d<NUM>)-<NUM>-(<NUM>-(methyl-d<NUM>) phenyl)pyridine(-<NUM>))<NUM>-(MeOH)<NUM>] trifluoromethanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv), <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylpropyl-<NUM>,<NUM>-d<NUM>)phenyl)-<NUM>-(naphtho[<NUM>,<NUM>-b]benzofuran-<NUM>-yl)pyridine ( <NUM>, <NUM> mmol, <NUM> equiv) and acetone (<NUM>) then the mixture was stirred for several minutes under a nitrogen atmosphere. Triethylamine (<NUM>, <NUM> mmol, <NUM> equiv) was added then the reaction mixture heated at <NUM> for <NUM> hours. The reaction mixture was removed from heat and allowed to cool to room temperature. The reaction mixture was filtered through a pad of Celite® (<NUM>), rinsing with dichloromethane (<NUM>). The filtrate was concentrated to give a red-orange solid which was triturated with <NUM>% dichloromethane in methanol (<NUM>) at <NUM> for one hour. The suspension was cooled to room temperature, filtered and the solid rinsed with methanol (<NUM>). The solid was dried in a vacuum oven overnight at <NUM> to give mer-complex (<NUM>) as an orange solid.

Crude compound after photoreaction (~<NUM>, wet) was filtered through a <NUM> inch pad of basic alumina atop a <NUM> inch pad of silica gel (<NUM> × <NUM> inch (wherein <NUM> inch = <NUM>)), eluting with dichloromethane (<NUM>). Product fractions were concentrated under reduced pressure to give a red-orange solid. The recovered material was purified on a Biotage automated chromatography system (<NUM> stacked <NUM> silica gel cartridges), eluting with <NUM>-<NUM>% tetrahydrofuran in hexanes. Cleanest product fractions concentrated under reduced pressure. The solid was precipitated from dichloromethane (<NUM>) with methanol (<NUM>) to give, after drying in a vacuum oven overnight at <NUM>, bis[<NUM>,<NUM>-bis(methyl-d<NUM>)-<NUM>-(<NUM>-(methyl-d<NUM>)phen-<NUM>'-yl)pyridin-<NUM>-yl][<NUM>-(<NUM>-(<NUM>,<NUM>-dimethylpropyl-<NUM>,<NUM>-d<NUM>)phenyl)-<NUM>-((naphtho[<NUM>,<NUM>-b]benzo-furan-<NUM>-yl)-<NUM>'-yl)pyridin-<NUM>-yl]Iridium(III) (<NUM>, <NUM>% yield, <NUM>% UPLC purity) as an orange solid.

All device examples were fabricated by high vacuum (<<NUM>-<NUM> Torr (<NUM> Torr = <NUM> Pa)) thermal evaporation (VTE). The anode electrode was <NUM>Å of indium tin oxide (ITO). The cathode consisted of <NUM>Å of LiQ (<NUM>-quinolinolato lithium) followed by <NUM>Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<<NUM> ppm of H<NUM>O and O<NUM>) 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, <NUM>Å of HATCN as the hole injection layer (HIL), <NUM>Å of hole transport material HTM as the hole transport layer (HTL), <NUM>Å of EBL as an electron blocking layer (EBL), <NUM>Å of <NUM> to <NUM> wt% emitter doped in a host as the emissive layer (EML) wherein the host comprised a <NUM>/<NUM> wt% mixture of H1/H2, and <NUM>Å of <NUM>% ETM in LiQ as the electron transport layer (ETL). As used herein, HATCN, HTM, EBL, H1, H2, and ETM have the following structures. Device structure is shown in the Table <NUM>, and the chemical structures of the device materials are shown below. <CHM>
<CHM>
<CHM>
<CHM>.

Claim 1:
A compound, Ir(LA)m(LB)<NUM>-m, having a structure of Formula I,
<CHM>
wherein
each of moiety A and moiety C is independently a <NUM>-membered carbocyclic or heterocyclic ring, a <NUM>-membered carbocyclic or heterocyclic ring, or a polycyclic fused ring system comprising <NUM>-membered and/or <NUM>-membered carbocyclic or heterocyclic rings;
moiety B is imidazole and Z<NUM> is N;
Z<NUM> is C or N;
m is <NUM> or <NUM>;
RA, RB, and RC each independently represent mono to the maximum allowable substitution, or no substitution;
at least one of R<NUM>, R<NUM>, R<NUM>, R<NUM> has a structure of Formula II,
<CHM>
or is a <NUM>-membered heterocyclic ring;
X<NUM> is CR1a or N, X<NUM> is CR2a or N, X<NUM> is CR3a or N, X<NUM> is CR4a or N, and X<NUM> is CR5a or N;
each of R<NUM>, R<NUM>, R<NUM>, R<NUM>, RA, RB, RC, R1a, R2a, R3a, R4a, and R5a is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, germyl, selenyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
at least one of R1a, R2a, R3a, R4a, R5a is selected from the group consisting of cycloalkyl, alkyl, silyl, germyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof;
if R<NUM> has Formula II, R3a is alkyl, and each of R1a, R2a, R4a, and R5a is H, then R3a is partially or fully deuterated or R3a comprises at least four carbon atoms; and
wherein any two substituents may be joined or fused to form a ring, with the provisos that R1a, R2a, R3a, R4a, and R5a do not form a <NUM>-membered ring.