# Patent

## Title
Organic electroluminescent materials and devices

## Abstract

Transition metal compounds having naphthalene imide moiety having enhanced electron withdrawing property and more metal-ligand charge transfer (MLCT) based excited state are disclosed. The disclosed compounds will improve the photoluminescent quantum yield (PLQY) and produce phosphorescent emission in red to near IR region which has many desired applications.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 62/816,590, filed on Mar. 11, 2019, the entire contents of which are incorporated herein by reference.


FIELD
The present invention relates to compounds for use as emitters, and devices, such as organic light emitting diodes, including the same.
BACKGROUND
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of 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. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
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. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
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 EML device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:




In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative) Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
SUMMARY
Disclosed herein are novel transition metal compounds comprising naphthalene imide moieties as emissive dopants for improving device performance of OLED devices. Transition metal compounds having naphthalene imide moiety as disclosed herein exhibit enhanced electron withdrawing property and the complexes are expected to show more metal-ligand charge transfer (MLCT) based excited state, which will improve the photoluminescent quantum yield (PLQY). The disclosed compounds are expected to produce phosphorescent emission in red to near IR region with good PLQYs and are useful as emitter materials in organic electroluminescence device.
A compound comprising a first ligand LA of Formula I




is disclosed.

In Formula I, T is a fused ring system comprising a structure of Formula II




ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; Z is C or N; RB represents mono to the maximum number of allowable substitutions, or no substitution; X1 to X6 are each C or N; each R, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituent defined herein; LA is complexed to a metal M to form a 5-membered chelate ring; M can be coordinated to other ligands; the ligand LA can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and any two substituents can be joined or fused together to form a ring.

An OLED comprising the compound of the present disclosure in an organic layer therein is also disclosed.
A consumer product comprising the OLED is also disclosed.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an organic light emitting device.
FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.
FIG. 3 shows photoluminescence (PL) spectrum of the inventive example compound Ir(LA35-4)2LC17-1 in 2-methylTHF.



DETAILED DESCRIPTION
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.
The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility 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 invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention 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 invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
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 “sulfinyl” refers to a —S(O)—RS radical.
The term “sulfonyl” refers to a —SO2—RS radical.
The term “phosphino” refers to a —P(RS)3 radical, wherein each RS can be same or different.
The term “silyl” refers to a —Si(RS)3 radical, wherein each RS can be same or different.
The term “boryl” refers to a —B(RS)2 radical or its Lewis adduct —B(RS)3 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, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group is optionally substituted.
The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group is 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, 0, S or N. Additionally, the heteroalkyl or heterocycloalkyl group is 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 is optionally substituted.
The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group is 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 is optionally substituted.
The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group is optionally substituted.
The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group is 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, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, 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, 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 R1 represents mono-substitution, then one R1 must be other than H (i.e., a substitution) Similarly, when R1 represents di-substitution, then two of R1 must be other than H. Similarly, when R1 represents no substitution, R1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.
As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.
A compound comprising a first ligand LA of Formula I




is disclosed.

In Formula I, T is a fused ring system comprising a structure of Formula II




ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; Z is C or N; RB represents mono to the maximum number of allowable substitutions, or no substitution; X1 to X6 are each C or N; each R, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituent defined herein; LA is complexed to a metal M to form a 5-membered chelate ring; M can be coordinated to other ligands; the ligand LA can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and any two substituents can be joined or fused together to form a ring.

The following options are applicable to any of the embodiments of the compound mentioned above. Each R, RA, and RB can be independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein. M can be selected from the group consisting of Os, Ir, Pd, and Pt. In one embodiment, M is Ir. In one embodiment, M is Pt. Two RA can be fused together to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring. Two RB can be fused together to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring. Adjacent RA and RB can be fused together to form a 6-membered carbocyclic or heterocyclic ring. Each of X1 to X6 can be C. One of X1 to X6 can be N, and the remainder can be C. Z can be N. Z can be C.
Except for the embodiments where two RB are fused together or adjacent RA and RB are fused together, each RB can be H.
The following options are applicable to any of the embodiments of the compound mentioned above. R can be selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl, and combinations thereof. Ring A can be a 6-membered aromatic ring. Ring A can be a benzene ring, which can be further substituted. RA can be selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and heteroaryl, and combinations thereof. M can be further coordinated to an acetylacetonate ligand, which can be further substituted.
In any of the embodiments of the compound mentioned above, the first ligand LA can be selected from the group consisting of:










where X7 to X12 are each C or N.

In any of the embodiments of the compound mentioned above, the first ligand LA can be selected from the group consisting of:
LAi-1, where i is an integer from 1 to 200, that are based on a structure of Formula 1




LAi-2, where i is an integer from 1 to 200, that are based on a structure of Formula 2





LAi-3, where i is an integer from 1 to 200, that are based on a structure of Formula 3





LAi-4, where i is an integer from 1 to 200, that are based on a structure of Formula 4





LAi-5, where i is an integer from 1 to 200, that are based on a structure of Formula 5





LAi-6, where i is an integer from 1 to 200, that are based on a structure of Formula 6





LAi-7, where i=an integer from 1 to 200, that are based on a structure of Formula 7





LAi-8, where I is an integer from 1 to 200, that are based on a structure of Formula 8





LAi-9, where i=an integer from 1 to 200, that are based on a structure of Formula 9





LAi-11, where i is an integer from 1 to 200, that are based on a structure of Formula 11





LAi-12, where i is an integer from 1 to 200, that are based on a structure of Formula 12





LAi-13, where i is an integer from 1 to 200, that are based on a structure of Formula 13





where for each LA1-1 to LA200-1, LA1-2 to LA200-2, LA1-3 to LA200-3, LA1-4 to LA200-4, LA1-5 to LA200-5, LA1-6 to LA200-6, LA1-7 to LA200-7, LA1-8 to LA200-8, LA1-9 to LA200-9, LA1-10 to LA200-10, LA1-11 to LA200-11, LA1-12 to LA200-12, LA1-13 to LA200-13, R and G have the following definitions for each i:













i
R
G

















1
R1
G1


2
R1
G2


3
R1
G3


4
R1
G4


5
R1
G5


6
R1
G6


7
R1
G7


8
R1
G8


9
R1
G9


10
R1
G10


11
R2
G1


12
R2
G2


13
R2
G3


14
R2
G4


15
R2
G5


16
R2
G6


17
R2
G7


18
R2
G8


19
R2
G9


20
R2
G10


21
R3
G1


22
R3
G2


23
R3
G3


24
R3
G4


25
R3
G5


26
R3
G6


27
R3
G7


28
R3
G8


29
R3
G9


30
R3
G10


31
R4
G1


32
R4
G2


33
R4
G3


34
R4
G4


35
R4
G5


36
R4
G6


37
R4
G7


38
R4
G8


39
R4
G9


40
R4
G10


41
R5
G1


42
R5
G2


43
R5
G3


44
R5
G4


45
R5
G5


46
R5
G6


47
R5
G7


48
R5
G8


49
R5
G9


50
R5
G10


51
R6
G1


52
R6
G2


53
R6
G3


54
R6
G4


55
R6
G5


56
R6
G6


57
R6
G7


58
R6
G8


59
R6
G9


60
R6
G10


61
R7
G1


62
R7
G2


63
R7
G3


64
R7
G4


65
R7
G5


66
R7
G6


67
R7
G7


68
R7
G8


69
R7
G9


70
R7
G10


71
R8
G1


72
R8
G2


73
R8
G3


74
R8
G4


75
R8
G5


76
R8
G6


77
R8
G7


78
R8
G8


79
R8
G9


80
R8
G10


81
R9
G1


82
R9
G2


83
R9
G3


84
R9
G4


85
R9
G5


86
R9
G6


87
R9
G7


88
R9
G8


89
R9
G9


90
R9
G10


91
R10
G1


92
R10
G2


93
R10
G3


94
R10
G4


95
R10
G5


96
R10
G6


97
R10
G7


98
R10
G8


99
R10
G9


100
R10
G10


101
R11
G1


102
R11
G2


103
R11
G3


104
R11
G4


105
R11
G5


106
R11
G6


107
R11
G7


108
R11
G8


109
R11
G9


110
R11
G10


111
R12
G1


112
R12
G2


113
R12
G3


114
R12
G4


115
R12
G5


116
R12
G6


117
R12
G7


118
R12
G8


119
R12
G9


120
R12
G10


121
R13
G1


122
R13
G2


123
R13
G3


124
R13
G4


125
R13
G5


126
R13
G6


127
R13
G7


128
R13
G8


129
R13
G9


130
R13
G10


131
R14
G1


132
R14
G2


133
R14
G3


134
R14
G4


135
R14
G5


136
R14
G6


137
R14
G7


138
R14
G8


139
R14
G9


140
R14
G10


141
R15
G1


142
R15
G2


143
R15
G3


144
R15
G4


145
R15
G5


146
R15
G6


147
R15
G7


148
R15
G8


149
R15
G9


150
R15
G10


151
R16
G1


152
R16
G2


153
R16
G3


154
R16
G4


155
R16
G5


156
R16
G6


157
R16
G7


158
R16
G8


159
R16
G9


160
R16
G10


161
R17
G1


162
R17
G2


163
R17
G3


164
R17
G4


165
R17
G5


166
R17
G6


167
R17
G7


168
R17
G8


169
R17
G9


170
R17
G10


171
R18
G1


172
R18
G2


173
R18
G3


174
R18
G4


175
R18
G5


176
R18
G6


177
R18
G7


178
R18
G8


179
R18
G9


180
R18
G10


181
R19
G1


182
R19
G2


183
R19
G3


184
R19
G4


185
R19
G5


186
R19
G6


187
R19
G7


188
R19
G8


189
R19
G9


190
R19
G10


191
R20
G1


192
R20
G2


193
R20
G3


194
R20
G4


195
R20
G5


196
R20
G6


197
R20
G7


198
R20
G8


199
R20
G9


200
R20
G10









LAi-10, where i is an integer from 201 to 240, that are based on a structure of Formula 10





where in each LA201-10 to LA240-10, R and RD have the following definitions for each i:













i
R
RD

















201
R1
H


202
R3
H


203
R5
H


204
R7
H


205
R9
H


206
R11
H


207
R13
H


208
R15
H


209
R17
H


210
R19
H


211
R1
CH3


212
R3
CH3


213
R5
CH3


214
R7
CH3


215
R9
CH3


216
R11
CH3


217
R13
CH3


218
R15
CH3


219
R17
CH3


220
R19
CH3


221
R2
H


222
R4
H


223
R6
H


224
R8
H


225
R10
H


226
R12
H


227
R14
H


228
R16
H


229
R18
H


230
R20
H


231
R2
CH3


232
R4
CH3


233
R6
CH3


234
R8
CH3


235
R10
CH3


236
R12
CH3


237
R14
CH3


238
R16
CH3


239
R18
CH3


240
R20
CH3









LAi-14, where i is an integer from 241 to 640, that are based on a structure of Formula 14





LAi-15, where i is an integer from 241 to 640, that are based on a structure of Formula 15





where in each LA241-14 to LA640-14, and LA241-15 to LA640-15, R, G, and R′ have the following definitions for each i:














i
R
G
R′


















241
R1
G1
CH3


242
R1
G2
CH3


243
R1
G3
CH3


244
R1
G4
CH3


245
R1
G5
CH3


246
R1
G6
CH3


247
R1
G7
CH3


248
R1
G8
CH3


249
R1
G9
CH3


250
R1
G10
CH3


251
R2
G1
CH3


252
R2
G2
CH3


253
R2
G3
CH3


254
R2
G4
CH3


255
R2
G5
CH3


256
R2
G6
CH3


257
R2
G7
CH3


258
R2
G8
CH3


259
R2
G9
CH3


260
R2
G10
CH3


261
R3
G1
CH3


262
R3
G2
CH3


263
R3
G3
CH3


264
R3
G4
CH3


265
R3
G5
CH3


266
R3
G6
CH3


267
R3
G7
CH3


268
R3
G8
CH3


269
R3
G9
CH3


270
R3
G10
CH3


271
R4
G1
CH3


272
R4
G2
CH3


273
R4
G3
CH3


274
R4
G4
CH3


275
R4
G5
CH3


276
R4
G6
CH3


277
R4
G7
CH3


278
R4
G8
CH3


279
R4
G9
CH3


280
R4
G10
CH3


281
R5
G1
CH3


282
R5
G2
CH3


283
R5
G3
CH3


284
R5
G4
CH3


285
R5
G5
CH3


286
R5
G6
CH3


287
R5
G7
CH3


288
R5
G8
CH3


289
R5
G9
CH3


290
R5
G10
CH3


291
R6
G1
CH3


292
R6
G2
CH3


293
R6
G3
CH3


294
R6
G4
CH3


295
R6
G5
CH3


296
R6
G6
CH3


297
R6
G7
CH3


298
R6
G8
CH3


299
R6
G9
CH3


300
R6
G10
CH3


301
R7
G1
CH3


302
R7
G2
CH3


303
R7
G3
CH3


304
R7
G4
CH3


305
R7
G5
CH3


306
R7
G6
CH3


307
R7
G7
CH3


308
R7
G8
CH3


309
R7
G9
CH3


310
R7
G10
CH3


311
R8
G1
CH3


312
R8
G2
CH3


313
R8
G3
CH3


314
R8
G4
CH3


315
R8
G5
CH3


316
R8
G6
CH3


317
R8
G7
CH3


318
R8
G8
CH3


319
R8
G9
CH3


320
R8
G10
CH3


321
R9
G1
CH3


322
R9
G2
CH3


323
R9
G3
CH3


324
R9
G4
CH3


325
R9
G5
CH3


326
R9
G6
CH3


327
R9
G7
CH3


328
R9
G8
CH3


329
R9
G9
CH3


330
R9
G10
CH3


331
R10
G1
CH3


332
R10
G2
CH3


333
R10
G3
CH3


334
R10
G4
CH3


335
R10
G5
CH3


336
R10
G6
CH3


337
R10
G7
CH3


338
R10
G8
CH3


339
R10
G9
CH3


340
R10
G10
CH3


341
R11
G1
CH3


342
R11
G2
CH3


343
R11
G3
CH3


344
R11
G4
CH3


345
R11
G5
CH3


346
R11
G6
CH3


347
R11
G7
CH3


348
R11
G8
CH3


349
R11
G9
CH3


350
R11
G10
CH3


351
R12
G1
CH3


352
R12
G2
CH3


353
R12
G3
CH3


354
R12
G4
CH3


355
R12
G5
CH3


356
R12
G6
CH3


357
R12
G7
CH3


358
R12
G8
CH3


359
R12
G9
CH3


360
R12
G10
CH3


361
R13
G1
CH3


362
R13
G2
CH3


363
R13
G3
CH3


364
R13
G4
CH3


365
R13
G5
CH3


366
R13
G6
CH3


367
R13
G7
CH3


368
R13
G8
CH3


369
R13
G9
CH3


370
R13
G10
CH3


371
R14
G1
CH3


372
R14
G2
CH3


373
R14
G3
CH3


374
R20
G10
CH(CH3)2


375
R14
G4
CH3


376
R14
G5
CH3


377
R14
G6
CH3


378
R14
G7
CH3


379
R14
G8
CH3


380
R14
G9
CH3


381
R14
G10
CH3


382
R15
G1
CH3


383
R15
G2
CH3


384
R15
G3
CH3


385
R15
G4
CH3


386
R15
G5
CH3


387
R15
G6
CH3


388
R15
G7
CH3


389
R15
G8
CH3


390
R15
G9
CH3


391
R15
G10
CH3


392
R16
G1
CH3


393
R16
G2
CH3


394
R16
G3
CH3


395
R16
G4
CH3


396
R16
G5
CH3


397
R16
G6
CH3


398
R16
G7
CH3


399
R16
G8
CH3


400
R16
G9
CH3


401
R16
G10
CH3


402
R17
G1
CH3


403
R17
G2
CH3


404
R17
G3
CH3


405
R17
G4
CH3


406
R17
G5
CH3


407
R17
G6
CH3


408
R17
G7
CH3


409
R17
G8
CH3


410
R17
G9
CH3


411
R17
G10
CH3


412
R18
G1
CH3


413
R18
G2
CH3


414
R18
G3
CH3


415
R18
G4
CH3


416
R18
G5
CH3


417
R18
G6
CH3


418
R18
G7
CH3


419
R18
G8
CH3


420
R18
G9
CH3


421
R18
G10
CH3


422
R19
G1
CH3


423
R19
G2
CH3


424
R19
G3
CH3


425
R19
G4
CH3


426
R19
G5
CH3


427
R19
G6
CH3


428
R19
G7
CH3


429
R19
G8
CH3


430
R19
G9
CH3


431
R19
G10
CH3


432
R20
G1
CH3


433
R20
G2
CH3


434
R20
G3
CH3


435
R20
G4
CH3


436
R20
G5
CH3


437
R20
G6
CH3


438
R20
G7
CH3


439
R20
G8
CH3


440
R20
G9
CH3


441
R20
G10
CH3


442
R1
G1
CH(CH3)2


443
R1
G2
CH(CH3)2


444
R1
G3
CH(CH3)2


445
R1
G4
CH(CH3)2


446
R1
G5
CH(CH3)2


447
R1
G6
CH(CH3)2


448
R1
G7
CH(CH3)2


449
R1
G8
CH(CH3)2


450
R1
G9
CH(CH3)2


451
R1
G10
CH(CH3)2


452
R2
G1
CH(CH3)2


453
R2
G2
CH(CH3)2


454
R2
G3
CH(CH3)2


455
R2
G4
CH(CH3)2


456
R2
G5
CH(CH3)2


457
R2
G6
CH(CH3)2


458
R2
G7
CH(CH3)2


459
R2
G8
CH(CH3)2


460
R2
G9
CH(CH3)2


461
R2
G10
CH(CH3)2


462
R3
G1
CH(CH3)2


463
R3
G2
CH(CH3)2


464
R3
G3
CH(CH3)2


465
R3
G4
CH(CH3)2


466
R3
G5
CH(CH3)2


467
R3
G6
CH(CH3)2


468
R3
G7
CH(CH3)2


469
R3
G8
CH(CH3)2


470
R3
G9
CH(CH3)2


471
R3
G10
CH(CH3)2


472
R4
G1
CH(CH3)2


473
R4
G2
CH(CH3)2


474
R4
G3
CH(CH3)2


475
R4
G4
CH(CH3)2


476
R4
G5
CH(CH3)2


477
R4
G6
CH(CH3)2


478
R4
G7
CH(CH3)2


479
R4
G8
CH(CH3)2


480
R4
G9
CH(CH3)2


481
R4
G10
CH(CH3)2


482
R5
G1
CH(CH3)2


483
R5
G2
CH(CH3)2


484
R5
G3
CH(CH3)2


485
R5
G4
CH(CH3)2


486
R5
G5
CH(CH3)2


487
R5
G6
CH(CH3)2


488
R5
G7
CH(CH3)2


489
R5
G8
CH(CH3)2


490
R5
G9
CH(CH3)2


491
R5
G10
CH(CH3)2


492
R6
G1
CH(CH3)2


493
R6
G2
CH(CH3)2


494
R6
G3
CH(CH3)2


495
R6
G4
CH(CH3)2


496
R6
G5
CH(CH3)2


497
R6
G6
CH(CH3)2


498
R6
G7
CH(CH3)2


499
R6
G8
CH(CH3)2


500
R6
G9
CH(CH3)2


501
R6
G10
CH(CH3)2


502
R7
G1
CH(CH3)2


503
R7
G2
CH(CH3)2


504
R7
G3
CH(CH3)2


505
R7
G4
CH(CH3)2


506
R7
G5
CH(CH3)2


507
R7
G6
CH(CH3)2


508
R7
G7
CH(CH3)2


509
R7
G8
CH(CH3)2


510
R7
G9
CH(CH3)2


511
R7
G10
CH(CH3)2


512
R8
G1
CH(CH3)2


513
R8
G2
CH(CH3)2


514
R8
G3
CH(CH3)2


515
R8
G4
CH(CH3)2


516
R8
G5
CH(CH3)2


517
R8
G6
CH(CH3)2


518
R8
G7
CH(CH3)2


519
R8
G8
CH(CH3)2


520
R8
G9
CH(CH3)2


521
R8
G10
CH(CH3)2


522
R9
G1
CH(CH3)2


523
R9
G2
CH(CH3)2


524
R9
G3
CH(CH3)2


525
R9
G4
CH(CH3)2


526
R9
G5
CH(CH3)2


527
R9
G6
CH(CH3)2


528
R9
G7
CH(CH3)2


529
R9
G8
CH(CH3)2


530
R9
G9
CH(CH3)2


531
R9
G10
CH(CH3)2


532
R10
G1
CH(CH3)2


533
R10
G2
CH(CH3)2


534
R10
G3
CH(CH3)2


535
R10
G4
CH(CH3)2


536
R10
G5
CH(CH3)2


537
R10
G6
CH(CH3)2


538
R10
G7
CH(CH3)2


539
R10
G8
CH(CH3)2


540
R10
G9
CH(CH3)2


541
R10
G10
CH(CH3)2


542
R11
G1
CH(CH3)2


543
R11
G2
CH(CH3)2


544
R11
G3
CH(CH3)2


545
R11
G4
CH(CH3)2


546
R11
G5
CH(CH3)2


547
R11
G6
CH(CH3)2


548
R11
G7
CH(CH3)2


549
R11
G8
CH(CH3)2


550
R11
G9
CH(CH3)2


551
R11
G10
CH(CH3)2


552
R12
G1
CH(CH3)2


553
R12
G2
CH(CH3)2


554
R12
G3
CH(CH3)2


555
R12
G4
CH(CH3)2


556
R12
G5
CH(CH3)2


557
R12
G6
CH(CH3)2


558
R12
G7
CH(CH3)2


559
R12
G8
CH(CH3)2


560
R12
G9
CH(CH3)2


561
R12
G10
CH(CH3)2


562
R13
G1
CH(CH3)2


563
R13
G2
CH(CH3)2


564
R13
G3
CH(CH3)2


565
R13
G4
CH(CH3)2


566
R13
G5
CH(CH3)2


567
R13
G6
CH(CH3)2


568
R13
G7
CH(CH3)2


569
R13
G8
CH(CH3)2


570
R13
G9
CH(CH3)2


571
R13
G10
CH(CH3)2


572
R14
G1
CH(CH3)2


573
R14
G2
CH(CH3)2


574
R14
G3
CH(CH3)2


575
R14
G4
CH(CH3)2


576
R14
G5
CH(CH3)2


577
R14
G6
CH(CH3)2


578
R14
G7
CH(CH3)2


579
R14
G8
CH(CH3)2


580
R14
G9
CH(CH3)2


581
R14
G10
CH(CH3)2


582
R15
G1
CH(CH3)2


583
R15
G2
CH(CH3)2


584
R15
G3
CH(CH3)2


585
R15
G4
CH(CH3)2


586
R15
G5
CH(CH3)2


587
R15
G6
CH(CH3)2


588
R15
G7
CH(CH3)2


589
R15
G8
CH(CH3)2


590
R15
G9
CH(CH3)2


591
R15
G10
CH(CH3)2


592
R16
G1
CH(CH3)2


593
R16
G2
CH(CH3)2


594
R16
G3
CH(CH3)2


595
R16
G4
CH(CH3)2


596
R16
G5
CH(CH3)2


597
R16
G6
CH(CH3)2


598
R16
G7
CH(CH3)2


599
R16
G8
CH(CH3)2


600
R16
G9
CH(CH3)2


601
R16
G10
CH(CH3)2


602
R17
G1
CH(CH3)2


603
R17
G2
CH(CH3)2


604
R17
G3
CH(CH3)2


605
R17
G4
CH(CH3)2


606
R17
G5
CH(CH3)2


607
R17
G6
CH(CH3)2


608
R17
G7
CH(CH3)2


609
R17
G8
CH(CH3)2


610
R17
G9
CH(CH3)2


611
R17
G10
CH(CH3)2


612
R18
G1
CH(CH3)2


613
R18
G2
CH(CH3)2


614
R18
G3
CH(CH3)2


615
R18
G4
CH(CH3)2


616
R18
G5
CH(CH3)2


617
R18
G6
CH(CH3)2


618
R18
G7
CH(CH3)2


619
R18
G8
CH(CH3)2


620
R18
G9
CH(CH3)2


621
R18
G10
CH(CH3)2


622
R19
G1
CH(CH3)2


623
R19
G2
CH(CH3)2


624
R19
G3
CH(CH3)2


625
R19
G4
CH(CH3)2


626
R19
G5
CH(CH3)2


627
R19
G6
CH(CH3)2


628
R19
G7
CH(CH3)2


629
R19
G8
CH(CH3)2


630
R19
G9
CH(CH3)2


631
R19
G10
CH(CH3)2


632
R20
G1
CH(CH3)2


633
R20
G2
CH(CH3)2


634
R20
G3
CH(CH3)2


635
R20
G4
CH(CH3)2


636
R20
G5
CH(CH3)2


637
R20
G6
CH(CH3)2


638
R20
G7
CH(CH3)2


639
R20
G8
CH(CH3)2


640
R20
G9
CH(CH3)2









where R1 to R20 have the following structures:








where G1 to G10 have the following structures:








In any of the embodiments of the compound mentioned above, the compound can have a formula of M(LA)x(LB)y(Lc)z where LA can be any of the LAs defined above, and LB and LC are each a bidentate ligand; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M. In some embodiments of the compound having the formula of M(LA)x(LB)y(LC)z, each LB can be independently selected from the group consisting of LB1 to LB263 whose structures are as follows






























































































































































and each LC can have the structure of LCj-I, having the structures based on Structure I





or LCj-II, having the structures based on Structure II





where j is an integer from 1 to 768; where for each LCj in LCj-I and LCj-II, R1 and R2 are defined as provided below:
















LCj
R1
R2









LC1
RD1
RD1



LC2
RD2
RD2



LC3
RD3
RD3



LC4
RD4
RD4



LC5
RD5
RD5



LC6
RD6
RD6



LC7
RD7
RD7



LC8
RD8
RD8



LC9
RD9
RD9



LC10
RD10
RD10



LC11
RD11
RD11



LC12
RD12
RD12



LC13
RD13
RD13



LC14
RD14
RD14



LC15
RD15
RD15



LC16
RD16
RD16



LC17
RD17
RD17



LC18
RD18
RD18



LC19
RD19
RD19



LC20
RD20
RD20



LC21
RD21
RD21



LC22
RD22
RD22



LC23
RD23
RD23



LC24
RD24
RD24



LC25
RD25
RD25



LC26
RD26
RD26



LC27
RD27
RD27



LC28
RD28
RD28



LC29
RD29
RD29



LC30
RD30
RD30



LC31
RD31
RD31



LC32
RD32
RD32



LC33
RD33
RD33



LC34
RD34
RD34



LC35
RD35
RD35



LC36
RD36
RD36



LC37
RD37
RD37



LC38
RD38
RD38



LC39
RD39
RD39



LC40
RD40
RD40



LC41
RD41
RD41



LC42
RD42
RD42



LC43
RD43
RD43



LC44
RD44
RD44



LC45
RD45
RD45



LC46
RD46
RD46



LC47
RD47
RD47



LC48
RD48
RD48



LC49
RD49
RD49



LC50
RD50
RD50



LC51
RD51
RD51



LC52
RD52
RD52



LC53
RD53
RD53



LC54
RD54
RD54



LC55
RD55
RD55



LC56
RD56
RD56



LC57
RD57
RD57



LC58
RD58
RD58



LC59
RD59
RD59



LC60
RD60
RD60



LC61
RD61
RD61



LC62
RD62
RD62



LC63
RD63
RD63



LC64
RD64
RD64



LC65
RD65
RD65



LC66
RD66
RD66



LC67
RD67
RD67



LC68
RD68
RD68



LC69
RD69
RD69



LC70
RD70
RD70



LC71
RD71
RD71



LC72
RD72
RD72



LC73
RD73
RD73



LC74
RD74
RD74



LC75
RD75
RD75



LC76
RD76
RD76



LC77
RD77
RD77



LC78
RD78
RD78



LC79
RD79
RD79



LC80
RD80
RD80



LC81
RD81
RD81



LC82
RD82
RD82



LC83
RD83
RD83



LC84
RD84
RD84



LC85
RD85
RD85



LC86
RD86
RD86



LC87
RD87
RD87



LC88
RD88
RD88



LC89
RD89
RD89



LC90
RD90
RD90



LC91
RD91
RD91



LC92
RD92
RD92



LC93
RD93
RD93



LC94
RD94
RD94



LC95
RD95
RD95



LC96
RD96
RD96



LC97
RD97
RD97



LC98
RD98
RD98



LC99
RD99
RD99



LC100
RD100
RD100



LC101
RD101
RD101



LC102
RD102
RD102



LC103
RD103
RD103



LC104
RD104
RD104



LC105
RD105
RD105



LC106
RD106
RD106



LC107
RD107
RD107



LC108
RD108
RD108



LC109
RD109
RD109



LC110
RD110
RD110



LC111
RD111
RD111



LC112
RD112
RD112



LC113
RD113
RD113



LC114
RD114
RD114



LC115
RD115
RD115



LC116
RD116
RD116



LC117
RD117
RD117



LC118
RD118
RD118



LC119
RD119
RD119



LC120
RD120
RD120



LC121
RD121
RD121



LC122
RD122
RD122



LC123
RD123
RD123



LC124
RD124
RD124



LC125
RD125
RD125



LC126
RD126
RD126



LC127
RD127
RD127



LC128
RD128
RD128



LC129
RD129
RD129



LC130
RD130
RD130



LC131
RD131
RD131



LC132
RD132
RD132



LC133
RD133
RD133



LC134
RD134
RD134



LC135
RD135
RD135



LC136
RD136
RD136



LC137
RD137
RD137



LC138
RD138
RD138



LC139
RD139
RD139



LC140
RD140
RD140



LC141
RD141
RD141



LC142
RD142
RD142



LC143
RD143
RD143



LC144
RD144
RD144



LC145
RD145
RD145



LC146
RD146
RD146



LC147
RD147
RD147



LC148
RD148
RD148



LC149
RD149
RD149



LC150
RD150
RD150



LC151
RD151
RD151



LC152
RD152
RD152



LC153
RD153
RD153



LC154
RD154
RD154



LC155
RD155
RD155



LC156
RD156
RD156



LC157
RD157
RD157



LC158
RD158
RD158



LC159
RD159
RD159



LC160
RD160
RD160



LC161
RD161
RD161



LC162
RD162
RD162



LC163
RD163
RD163



LC164
RD164
RD164



LC165
RD165
RD165



LC166
RD166
RD166



LC167
RD167
RD167



LC168
RD168
RD168



LC169
RD169
RD169



LC170
RD170
RD170



LC171
RD171
RD171



LC172
RD172
RD172



LC173
RD173
RD173



LC174
RD174
RD174



LC175
RD175
RD175



LC176
RD176
RD176



LC177
RD177
RD177



LC178
RD178
RD178



LC179
RD179
RD179



LC180
RD180
RD180



LC181
RD181
RD181



LC182
RD182
RD182



LC183
RD183
RD183



LC184
RD184
RD184



LC185
RD185
RD185



LC186
RD186
RD186



LC187
RD187
RD187



LC188
RD188
RD188



LC189
RD189
RD189



LC190
RD190
RD190



LC191
RD191
RD191



LC192
RD192
RD192



LC193
RD1
RD3



LC194
RD1
RD4



LC195
RD1
RD5



LC196
RD1
RD9



LC197
RD1
RD10



LC198
RD1
RD17



LC199
RD1
RD18



LC200
RD1
RD20



LC201
RD1
RD22



LC202
RD1
RD37



LC203
RD1
RD40



LC204
RD1
RD41



LC205
RD1
RD42



LC206
RD1
RD43



LC207
RD1
RD48



LC208
RD1
RD49



LC209
RD1
RD50



LC210
RD1
RD54



LC211
RD1
RD55



LC212
RD1
RD58



LC213
RD1
RD59



LC214
RD1
RD78



LC215
RD1
RD79



LC216
RD1
RD81



LC217
RD1
RD87



LC218
RD1
RD88



LC219
RD1
RD89



LC220
RD1
RD93



LC221
RD1
RD116



LC222
RD1
RD117



LC223
RD1
RD118



LC224
RD1
RD119



LC225
RD1
RD120



LC226
RD1
RD133



LC227
RD1
RD134



LC228
RD1
RD135



LC229
RD1
RD136



LC230
RD1
RD143



LC231
RD1
RD144



LC232
RD1
RD145



LC233
RD1
RD146



LC234
RD1
RD147



LC235
RD1
RD149



LC236
RD1
RD151



LC237
RD1
RD154



LC238
RD1
RD155



LC239
RD1
RD161



LC240
RD1
RD175



LC241
RD4
RD3



LC242
RD4
RD5



LC243
RD4
RD9



LC244
RD4
RD10



LC245
RD4
RD17



LC246
RD4
RD18



LC247
RD4
RD20



LC248
RD4
RD22



LC249
RD4
RD37



LC250
RD4
RD40



LC251
RD4
RD41



LC252
RD4
RD42



LC253
RD4
RD43



LC254
RD4
RD48



LC255
RD4
RD49



LC256
RD4
RD50



LC257
RD4
RD54



LC258
RD4
RD55



LC259
RD4
RD58



LC260
RD4
RD59



LC261
RD4
RD78



LC262
RD4
RD79



LC263
RD4
RD81



LC264
RD4
RD87



LC265
RD4
RD88



LC266
RD4
RD89



LC267
RD4
RD93



LC268
RD4
RD116



LC269
RD4
RD117



LC270
RD4
RD118



LC271
RD4
RD119



LC272
RD4
RD120



LC273
RD4
RD133



LC274
RD4
RD134



LC275
RD4
RD135



LC276
RD4
RD136



LC277
RD4
RD143



LC278
RD4
RD144



LC279
RD4
RD145



LC280
RD4
RD146



LC281
RD4
RD147



LC282
RD4
RD149



LC283
RD4
RD151



LC284
RD4
RD154



LC285
RD4
RD155



LC286
RD4
RD161



LC287
RD4
RD175



LC288
RD9
RD3



LC289
RD9
RD5



LC290
RD9
RD10



LC291
RD9
RD17



LC292
RD9
RD18



LC293
RD9
RD20



LC294
RD9
RD22



LC295
RD9
RD37



LC296
RD9
RD40



LC297
RD9
RD41



LC298
RD9
RD42



LC299
RD9
RD43



LC300
RD9
RD48



LC301
RD9
RD49



LC302
RD9
RD50



LC303
RD9
RD54



LC304
RD9
RD55



LC305
RD9
RD58



LC306
RD9
RD59



LC307
RD9
RD78



LC308
RD9
RD79



LC309
RD9
RD81



LC310
RD9
RD87



LC311
RD9
RD88



LC312
RD9
RD89



LC313
RD9
RD93



LC314
RD9
RD116



LC315
RD9
RD117



LC316
RD9
RD118



LC317
RD9
RD119



LC318
RD9
RD120



LC319
RD9
RD133



LC320
RD9
RD134



LC321
RD9
RD135



LC322
RD9
RD136



LC323
RD9
RD143



LC324
RD9
RD144



LC325
RD9
RD145



LC326
RD9
RD146



LC327
RD9
RD147



LC328
RD9
RD149



LC329
RD9
RD151



LC330
RD9
RD154



LC331
RD9
RD155



LC332
RD9
RD161



LC333
RD9
RD175



LC334
RD10
RD3



LC335
RD10
RD5



LC336
RD10
RD17



LC337
RD10
RD18



LC338
RD10
RD20



LC339
RD10
RD22



LC340
RD10
RD37



LC341
RD10
RD40



LC342
RD10
RD41



LC343
RD10
RD42



LC344
RD10
RD43



LC345
RD10
RD48



LC346
RD10
RD49



LC347
RD10
RD50



LC348
RD10
RD54



LC349
RD10
RD55



LC350
RD10
RD58



LC351
RD10
RD59



LC352
RD10
RD78



LC353
RD10
RD79



LC354
RD10
RD81



LC355
RD10
RD87



LC356
RD10
RD88



LC357
RD10
RD89



LC358
RD10
RD93



LC359
RD10
RD116



LC360
RD10
RD117



LC361
RD10
RD118



LC362
RD10
RD119



LC363
RD10
RD120



LC364
RD10
RD133



LC365
RD10
RD134



LC366
RD10
RD135



LC367
RD10
RD136



LC368
RD10
RD143



LC369
RD10
RD144



LC370
RD10
RD145



LC371
RD10
RD146



LC372
RD10
RD147



LC373
RD10
RD149



LC374
RD10
RD151



LC375
RD10
RD154



LC376
RD10
RD155



LC377
RD10
RD161



LC378
RD10
RD175



LC379
RD17
RD3



LC380
RD17
RD5



LC381
RD17
RD18



LC382
RD17
RD20



LC383
RD17
RD22



LC384
RD17
RD37



LC385
RD17
RD40



LC386
RD17
RD41



LC387
RD17
RD42



LC388
RD17
RD43



LC389
RD17
RD48



LC390
RD17
RD49



LC391
RD17
RD50



LC392
RD17
RD54



LC393
RD17
RD55



LC394
RD17
RD58



LC395
RD17
RD59



LC396
RD17
RD78



LC397
RD17
RD79



LC398
RD17
RD81



LC399
RD17
RD87



LC400
RD17
RD88



LC401
RD17
RD89



LC402
RD17
RD93



LC403
RD17
RD116



LC404
RD17
RD117



LC405
RD17
RD118



LC406
RD17
RD119



LC407
RD17
RD120



LC408
RD17
RD133



LC409
RD17
RD134



LC410
RD17
RD135



LC411
RD17
RD136



LC412
RD17
RD143



LC413
RD17
RD144



LC414
RD17
RD145



LC415
RD17
RD146



LC416
RD17
RD147



LC417
RD17
RD149



LC418
RD17
RD151



LC419
RD17
RD154



LC420
RD17
RD155



LC421
RD17
RD161



LC422
RD17
RD175



LC423
RD50
RD3



LC424
RD50
RD5



LC425
RD50
RD18



LC426
RD50
RD20



LC427
RD50
RD22



LC428
RD50
RD37



LC429
RD50
RD40



LC430
RD50
RD41



LC431
RD50
RD42



LC432
RD50
RD43



LC433
RD50
RD48



LC434
RD50
RD49



LC435
RD50
RD54



LC436
RD50
RD55



LC437
RD50
RD58



LC438
RD50
RD59



LC439
RD50
RD78



LC440
RD50
RD79



LC441
RD50
RD81



LC442
RD50
RD87



LC443
RD50
RD88



LC444
RD50
RD89



LC445
RD50
RD93



LC446
RD50
RD116



LC447
RD50
RD117



LC448
RD50
RD118



LC449
RD50
RD119



LC450
RD50
RD120



LC451
RD50
RD133



LC452
RD50
RD134



LC453
RD50
RD135



LC454
RD50
RD136



LC455
RD50
RD143



LC456
RD50
RD144



LC457
RD50
RD145



LC458
RD50
RD146



LC459
RD50
RD147



LC460
RD50
RD149



LC461
RD50
RD151



LC462
RD50
RD154



LC463
RD50
RD155



LC464
RD50
RD161



LC465
RD50
RD175



LC466
RD55
RD3



LC467
RD55
RD5



LC468
RD55
RD18



LC469
RD55
RD20



LC470
RD55
RD22



LC471
RD55
RD37



LC472
RD55
RD40



LC473
RD55
RD41



LC474
RD55
RD42



LC475
RD55
RD43



LC476
RD55
RD48



LC477
RD55
RD49



LC478
RD55
RD54



LC479
RD55
RD58



LC480
RD55
RD59



LC481
RD55
RD78



LC482
RD55
RD79



LC483
RD55
RD81



LC484
RD55
RD87



LC485
RD55
RD88



LC486
RD55
RD89



LC487
RD55
RD93



LC488
RD55
RD116



LC489
RD55
RD117



LC490
RD55
RD118



LC491
RD55
RD119



LC492
RD55
RD120



LC493
RD55
RD133



LC494
RD55
RD134



LC495
RD55
RD135



LC496
RD55
RD136



LC497
RD55
RD143



LC498
RD55
RD144



LC499
RD55
RD145



LC500
RD55
RD146



LC501
RD55
RD147



LC502
RD55
RD149



LC503
RD55
RD151



LC504
RD55
RD154



LC505
RD55
RD155



LC506
RD55
RD161



LC507
RD55
RD175



LC508
RD116
RD3



LC509
RD116
RD5



LC510
RD116
RD17



LC511
RD116
RD18



LC512
RD116
RD20



LC513
RD116
RD22



LC514
RD116
RD37



LC515
RD116
RD40



LC516
RD116
RD41



LC517
RD116
RD42



LC518
RD116
RD43



LC519
RD116
RD48



LC520
RD116
RD49



LC521
RD116
RD54



LC522
RD116
RD58



LC523
RD116
RD59



LC524
RD116
RD78



LC525
RD116
RD79



LC526
RD116
RD81



LC527
RD116
RD87



LC528
RD116
RD88



LC529
RD116
RD89



LC530
RD116
RD93



LC531
RD116
RD117



LC532
RD116
RD118



LC533
RD116
RD119



LC534
RD116
RD120



LC535
RD116
RD133



LC536
RD116
RD134



LC537
RD116
RD135



LC538
RD116
RD136



LC539
RD116
RD143



LC540
RD116
RD144



LC541
RD116
RD145



LC542
RD116
RD146



LC543
RD116
RD147



LC544
RD116
RD149



LC545
RD116
RD151



LC546
RD116
RD154



LC547
RD116
RD155



LC548
RD116
RD161



LC549
RD116
RD175



LC550
RD143
RD3



LC551
RD143
RD5



LC552
RD143
RD17



LC553
RD143
RD18



LC554
RD143
RD20



LC555
RD143
RD22



LC556
RD143
RD37



LC557
RD143
RD40



LC558
RD143
RD41



LC559
RD143
RD42



LC560
RD143
RD43



LC561
RD143
RD48



LC562
RD143
RD49



LC563
RD143
RD54



LC564
RD143
RD58



LC565
RD143
RD59



LC566
RD143
RD78



LC567
RD143
RD79



LC568
RD143
RD81



LC569
RD143
RD87



LC570
RD143
RD88



LC571
RD143
RD89



LC572
RD143
RD93



LC573
RD143
RD116



LC574
RD143
RD117



LC575
RD143
RD118



LC576
RD143
RD119



LC577
RD143
RD120



LC578
RD143
RD133



LC579
RD143
RD134



LC580
RD143
RD135



LC581
RD143
RD136



LC582
RD143
RD144



LC583
RD143
RD145



LC584
RD143
RD146



LC585
RD143
RD147



LC586
RD143
RD149



LC587
RD143
RD151



LC588
RD143
RD154



LC589
RD143
RD155



LC590
RD143
RD161



LC591
RD143
RD175



LC592
RD144
RD3



LC593
RD144
RD5



LC594
RD144
RD17



LC595
RD144
RD18



LC596
RD144
RD20



LC597
RD144
RD22



LC598
RD144
RD37



LC599
RD144
RD40



LC600
RD144
RD41



LC601
RD144
RD42



LC602
RD144
RD43



LC603
RD144
RD48



LC604
RD144
RD49



LC605
RD144
RD54



LC606
RD144
RD58



LC607
RD144
RD59



LC608
RD144
RD78



LC609
RD144
RD79



LC610
RD144
RD81



LC611
RD144
RD87



LC612
RD144
RD88



LC613
RD144
RD89



LC614
RD144
RD93



LC615
RD144
RD116



LC616
RD144
RD117



LC617
RD144
RD118



LC618
RD144
RD119



LC619
RD144
RD120



LC620
RD144
RD133



LC621
RD144
RD134



LC622
RD144
RD135



LC623
RD144
RD136



LC624
RD144
RD145



LC625
RD144
RD146



LC626
RD144
RD147



LC627
RD144
RD149



LC628
RD144
RD151



LC629
RD144
RD154



LC630
RD144
RD155



LC631
RD144
RD161



LC632
RD144
RD175



LC633
RD145
RD3



LC634
RD145
RD5



LC635
RD145
RD17



LC636
RD145
RD18



LC637
RD145
RD20



LC638
RD145
RD22



LC639
RD145
RD37



LC640
RD145
RD40



LC641
RD145
RD41



LC642
RD145
RD42



LC643
RD145
RD43



LC644
RD145
RD48



LC645
RD145
RD49



LC646
RD145
RD54



LC647
RD145
RD58



LC648
RD145
RD59



LC649
RD145
RD78



LC650
RD145
RD79



LC651
RD145
RD81



LC652
RD145
RD87



LC653
RD145
RD88



LC654
RD145
RD89



LC655
RD145
RD93



LC656
RD145
RD116



LC657
RD145
RD117



LC658
RD145
RD118



LC659
RD145
RD119



LC660
RD145
RD120



LC661
RD145
RD133



LC662
RD145
RD134



LC663
RD145
RD135



LC664
RD145
RD136



LC665
RD145
RD146



LC666
RD145
RD147



LC667
RD145
RD149



LC668
RD145
RD151



LC669
RD145
RD154



LC670
RD145
RD155



LC671
RD145
RD161



LC672
RD145
RD175



LC673
RD146
RD3



LC674
RD146
RD5



LC675
RD146
RD17



LC676
RD146
RD18



LC677
RD146
RD20



LC678
RD146
RD22



LC679
RD146
RD37



LC680
RD146
RD40



LC681
RD146
RD41



LC682
RD146
RD42



LC683
RD146
RD43



LC684
RD146
RD48



LC685
RD146
RD49



LC686
RD146
RD54



LC687
RD146
RD58



LC688
RD146
RD59



LC689
RD146
RD78



LC690
RD146
RD79



LC691
RD146
RD81



LC692
RD146
RD87



LC693
RD146
RD88



LC694
RD146
RD89



LC695
RD146
RD93



LC696
RD146
RD117



LC697
RD146
RD118



LC698
RD146
RD119



LC699
RD146
RD120



LC700
RD146
RD133



LC701
RD146
RD134



LC702
RD146
RD135



LC703
RD146
RD136



LC704
RD146
RD146



LC705
RD146
RD147



LC706
RD146
RD149



LC707
RD146
RD151



LC708
RD146
RD154



LC709
RD146
RD155



LC710
RD146
RD161



LC711
RD146
RD175



LC712
RD133
RD3



LC713
RD133
RD5



LC714
RD133
RD3



LC715
RD133
RD18



LC716
RD133
RD20



LC717
RD133
RD22



LC718
RD133
RD37



LC719
RD133
RD40



LC720
RD133
RD41



LC721
RD133
RD42



LC722
RD133
RD43



LC723
RD133
RD48



LC724
RD133
RD49



LC725
RD133
RD54



LC726
RD133
RD58



LC727
RD133
RD59



LC728
RD133
RD78



LC729
RD133
RD79



LC730
RD133
RD81



LC731
RD133
RD87



LC732
RD133
RD88



LC733
RD133
RD89



LC734
RD133
RD93



LC735
RD133
RD117



LC736
RD133
RD118



LC737
RD133
RD119



LC738
RD133
RD120



LC739
RD133
RD133



LC740
RD133
RD134



LC741
RD133
RD135



LC742
RD133
RD136



LC743
RD133
RD146



LC744
RD133
RD147



LC745
RD133
RD149



LC746
RD133
RD151



LC747
RD133
RD154



LC748
RD133
RD155



LC749
RD133
RD161



LC750
RD133
RD175



LC751
RD175
RD3



LC752
RD175
RD5



LC753
RD175
RD18



LC754
RD175
RD20



LC755
RD175
RD22



LC756
RD175
RD37



LC757
RD175
RD40



LC758
RD175
RD41



LC759
RD175
RD42



LC760
RD175
RD43



LC761
RD175
RD48



LC762
RD175
RD49



LC763
RD175
RD54



LC764
RD175
RD58



LC765
RD175
RD59



LC766
RD175
RD78



LC767
RD175
RD79



LC768
RD175
RD81










where RD1 to RD192 have the following structures:


















































In any of the embodiments of the compound mentioned above, when M is Ir, the compound can have a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), Ir(LA)2(LC), and Ir(LA)(LB)(LC); and wherein LA, LB, and LC are different from each other. LA, LB, and LC can be any of the structures defined above for LA, LB, and LC.
In any of the embodiments of the compound mentioned above, when M is Pt, the compound can have a formula of Pt(LA)(LB), where LA and LB can be same or different. LA and LB can be connected to form a tetradentate ligand. LA and LB can be any of the structures defined above for LA and LB.
In the embodiments of the compound having the formula of M(LA)x(LB)y(LC)z where LB and LC are each a bidentate ligand; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M, each LB and LC can be independently selected from the group consisting of:










where, each Y1 to Y13 is independently selected from the group consisting of carbon and nitrogen; Y′ is selected from the group consisting of B Re, N Re, P Re, O, S, Se, C═O, S═O, SO2, CReRf, SiReRf, and GeReRf; Re and Rf can be fused or joined to form a ring; each Ra, Rb, Re, and Rd independently represents from mono substitution to the maximum possible number of substitutions, or no substitution; each Ra, Rb, Rc, Rd, Re and Rf is independently a hydroge or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and any two adjacent substituents of Ra, Rb, Rc, and Rd can be fused or joined to form a ring or form a multidentate ligand. In such embodiments of the compound, each LB and LC can be independently selected from the group consisting of:














In the embodiments of the compound having a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), Ir(LA)2(LC), and Ir(LA)(LB)(LC); and wherein LA, LB, and LC are different from each other, the compound can be Compound Ax-F having the formula Ir(LAi-f)3, Compound By-F having the formula Ir(LAi-f)(LBk)2, or Compound Cz-F having the formula Ir(LAi-f)2(LCj);
where x=i, F=f, y=263i+k−263, and z=768i+j−768;
where i is an integer from 1 to 640, f is an integer from 1 to 15, and k is an integer from 1 to 263, and j is an integer from 1 to 768;
where LBk have the structures LB1 to LB263; and
LCj can have one of the structures LCj-I and LCj-II defined above.
An organic light emitting device (OLED) incorporating the novel compound of the present disclosure is also disclosed. The OLED comprises: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand LA of Formula I




where, T is a fused ring system that comprises a structure of Formula II





ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; Z is C or N; RB represents mono to the maximum number of allowable substitutions, or no substitution; X1 to X6 are each C or N; each R, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; LA is complexed to a metal M to form a 5-membered chelate ring; M can be coordinated to other ligands; and the ligand LA can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and any two substituents can be joined or fused together to form a ring.

In some embodiments of the OLED, the organic layer is an emissive layer and the compound can be an emissive dopant or a non-emissive dopant. In some embodiments of the OLED, the organic layer further comprises a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. In some embodiments, the host can be selected from the group consisting of:













and combinations thereof. The OLED of claim 26, wherein the organic layer further comprises a host, wherein the host comprises a metal complex.

A consumer product comprising such OLED is also disclosed. The OLED comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand LA of Formula I




where, T is a fused ring system that comprises a structure of Formula II





ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; Z is C or N; RB represents mono to the maximum number of allowable substitutions, or no substitution; X1 to X6 are each C or N; each R, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; LA is complexed to a metal M to form a 5-membered chelate ring; M can be coordinated to other ligands; and the ligand LA can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and

any two substituents can be joined or fused together to form a ring.

In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, published on Mar. 14, 2019 as U.S. patent application publication No. 2019/0081248, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others).
When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligand(s). In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.
In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter.
In some embodiments, the compound of the present disclosure is neutrally charged.
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.
The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═C5-CnH2n+1, C≡C—CnH2n+1, Ar1—Ar2, and CnH2n—Ar1, or the host has no substitutions. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound, for example, a Zn containing inorganic material e.g. ZnS.
The host can be a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be, but is not limited to, a specific compound selected from the Host Group consisting of:













and combinations thereof.

Additional information on possible hosts is provided below.

An emissive region in an OLED is also disclosed. The emissive region comprising a compound comprising a first ligand LA of Formula I




where, T is a fused ring system that comprises a structure of Formula II





ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; Z is C or N; RB represents mono to the maximum number of allowable substitutions, or no substitution; X1 to X6 are each C or N; each R, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; LA is complexed to a metal M to form a 5-membered chelate ring; M can be coordinated to other ligands; and the ligand LA can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and

any two substituents can be joined or fused together to form a ring.

In some embodiments of the emissive region, the compound can be an emissive dopant or a non-emissive dopant. The emissive region can further comprise a host, where the host contains at least one group selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
Where the emissive region further comprises a host, the host can be selected from the group consisting of:













and combinations thereof.

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 is can also be incorporated into the supramolecule complex without covalent bonds.
Combination with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination. Conductivity Dopants:
A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.







HIL/HTL:

A hole injecting/transporting material to be used in the present invention 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 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:




Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:




wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:




wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k′′ is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.




















































EBL:

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
Host:
The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:




wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k′′ is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:




wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:







wherein R101 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 0 to 20 or 1 to 20. X101 to X108 are independently selected from C (including CH) or N. Z101 and Z102 are independently selected from NR101, O, or S.

Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,































Additional Emitters:

One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.
































































HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:




wherein k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:




wherein R101 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. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:




wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,



















Charge Generation Layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. 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.
EXPERIMENTAL




NBS (305 g, 1712 mmol) was added portion wise to a solution of methyl 1H-indole-4-carboxylate (100 g, 571 mmol) in t-BuOH (2283 mL) at room temperature for 1 hour. After 3 hours, the solvent was removed, and the residue was dissolved in mixed solvents of MeOH/H2O and refluxed for about 16 hours. After cooling down, the reaction mixture was filtered, and the filtrate was extracted with DCM. Combined organic layer was dried over MgSO4 and filtered. The solvent was removed, and the residue was stirred in ethyl acetate (150 mL), and the product was collected by filtration (55 g).




Methyl 2,3-dioxoindoline-4-carboxylate (35 g, 171 mmol) was dissolved in acetic anhydride (80 mL) and heated to 80-90° C. for 2 hours. Then, the solvent was removed, and the residue was triturated in ether to give 33 g of product in 78% yield.




A solution of methyl 1-acetyl-2,3-dioxoindoline-4-carboxylate (32 g, 129 mmol) in NaOH (64.7 mL, 4N, 259 mmol) was heated to 90° C. for 1 hour. The reaction mixture was then quenched with HCl. The precipitate was collected by filtration, and then dried. 24.79 g of desired product was obtained in 89% yield.




Isopropylamine (24.66 mL, 287 mmol) was added slowly to a solution of 1H,4H-pyrano[3,4,5-de]quinoline-2,4,6-trione (24.7 g, 115 mmol) in acetic acid (500 mL), and then heated to 120° C. for 32 hours. After cooling down, the reaction mixture was poured into ice water (500 g). The precipitate was collected by filtration and dried. 11 g of product was obtained in 35% yield.




POCl3 (20 mL, 215 mmol) was added to a solution of 5-isopropyl-1H-benzo[de][2,6]naphthyridine-2,4,6(5H)-trione (11 g, 42.9 mmol) in dioxane (300 mL). The reaction mixture was heated to reflux for about 16 hours. After cooling down, the solvent was removed, and the residue was dissolved in acetonitrile and quenched with ice. The precipitate was collected and recrystallized from acetonitrile to give 7 g of product in 59% yield.




A 500 mL RBF (round bottom flask) was charged with 2-chloro-5-isopropyl-4H-benzo[de][2,6]naphthyridine-4,6(5H)-dione (2 g, 7.28 mmol), (4-(tert-butyl)naphthalen-2-yl)boronic acid (2.159 g, 9.46 mmol), potassium phosphate monohydrate (3.35 g, 14.56 mmol), THF (72.8 ml), X-Phos G3 precat (0.308 g, 0.364 mmol) and dicyclohexyl(2′,4′,6′-triisopropyl-[1,1′-biphenyl]-2-yl)phosphane (0.174 g, 0.364 mmol) and the reaction was degassed with nitrogen. The white suspension was heated at 50° C. for about 16 hours. After the reaction, the solvent was removed and the residue was purified on a silica gel column to give the product.




2-(4-(tert-butypnaphthalen-2-yl)-5-isopropyl-4H-benzo[de][2,6]naphthyridine-4,6(5H)-dione (1.032 g, 2.442 mmol) and IrCl3 (0.4 g) were added in an organic solvent (30 ml). The mixture was degassed by N2 for 20 minutes and then heated up to 130° C. After the reaction mixture was cooled to room temperature, it was used directly in the next step reaction.




The reaction mixture from the previous step was added to 3,7-diethylnonane-4,6-dione (0.62 g, 2.97 mmol), potassium carbonate (0.40 g, 2.97 mmol), and THF (20 mL). The mixture was degassed by N2 and heated at 50 degree for 15 hours. After the solvent was removed, the residue was purified on silica gel column to give product. LCMS M/Z=1246.
FIG. 3 shows photoluminescence spectrum of the inventive example Ir(LA35-4)2LC17-I in 2-methylTHF. The compound shows broad emission in the near-IR region extending to beyond 1100 nm. The compound can be used as a near-IR emitter in organic electroluminescent device applications.
It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

## Claims

1. A compound comprising a first ligand LA of Formula I



wherein,
T is a fused ring system that comprises a structure of Formula II




ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
Z is C or N;
RB represents mono to the maximum number of allowable substitutions, or no substitution;
X1 to X6 are each C or N;
each R, RA, and RB is independently a 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;
when ring A bonds to X3 or X4, at least one of the following is true:
at least one of X1-X6 is N;
Z is C;
R is a hydrogen or a substituent selected from the group consisting of deuterium, halogen, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;

LA is complexed to a metal M to form a 5-membered chelate ring;
M can be coordinated to other ligands; and
the ligand LA can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate,
or hexadentate ligand; and
any two substituents can be joined or fused together to form a ring.

2. The compound of claim 1, wherein each R, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.

3. The compound of claim 1, wherein M is selected from the group consisting of Os, Ir, Pd, and Pt.

4. The compound of claim 1, wherein two RA are fused together to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring.

5. The compound of claim 1, wherein two RB are fused together to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring.

6. The compound of claim 1, wherein adjacent RA and RB are fused together to form a 6-membered carbocyclic or heterocyclic ring.

7. The compound of claim 1, wherein X1 to X6 are each C.

8. The compound of claim 1, wherein one of X1 to X6 is N, and the remainder are C.

9. The compound of claim 1, wherein R is selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl, and combinations thereof.

10. The compound of claim 1, wherein ring A is a 6-membered aromatic ring.

11. The compound of claim 1, wherein the first ligand LA is selected from the group consisting of:










wherein X7 to X12 are each C or N.

12. The compound of claim 1, wherein the first ligand LA is selected from the group consisting of:
LAi-1, wherein i=an integer from 1 to 200, that are based on a structure of Formula 1




LAi-2, wherein i=an integer from 1 to 200, that are based on a structure of Formula 2




LAi-3, wherein i=an integer from 1 to 200, that are based on a structure of Formula 3




LAi-4, wherein i=an integer from 1 to 200, that are based on a structure of Formula 4




LAi-5, wherein i=an integer from 1 to 200, that are based on a structure of Formula 5




LAi-6, wherein i=an integer from 1 to 200, that are based on a structure of Formula 6




LAi-7, wherein i=an integer from 1 to 200, that are based on a structure of Formula 7




LAi-8, wherein i=an integer from 1 to 200, that are based on a structure of Formula 8




LAi-9, wherein i=an integer from 1 to 200, that are based on a structure of Formula 9




LAi-11, wherein i=an integer from 1 to 200, that are based on a structure of Formula 11




LAi-12, wherein i=an integer from 1 to 200, that are based on a structure of Formula 12




LAi-13, wherein i=an integer from 1 to 200, that are based on a structure of Formula 13




wherein for each LA1-1 to LA200-1, LA1-2 to LA200-2, LA1-3 to LA200-3, LA1-4 to LA200-4, LA1-5 to LA200-5, LA1-6 to LA200-6, LA1-7 to LA200-7, LA1-8 to LA200-8, LA1-9 to LA200-9, LA1-10 to LA200-10, LA1-11 to LA200-11, LA1-12 to LA200-12, LA1-13 to LA200-13, R and G have the following definitions for each i:













i
R
G

















1
R1
G1


2
R1
G2


3
R1
G3


4
R1
G4


5
R1
G5


6
R1
G6


7
R1
G7


8
R1
G8


9
R1
G9


10
R1
G10


11
R2
G1


12
R2
G2


13
R2
G3


14
R2
G4


15
R2
G5


16
R2
G6


17
R2
G7


18
R2
G8


19
R2
G9


20
R2
G10


21
R3
G1


22
R3
G2


23
R3
G3


24
R3
G4


25
R3
G5


26
R3
G6


27
R3
G7


28
R3
G8


29
R3
G9


30
R3
G10


31
R4
G1


32
R4
G2


33
R4
G3


34
R4
G4


35
R4
G5


36
R4
G6


37
R4
G7


38
R4
G8


39
R4
G9


40
R4
G10


41
R5
G1


42
R5
G2


43
R5
G3


44
R5
G4


45
R5
G5


46
R5
G6


47
R5
G7


48
R5
G8


49
R5
G9


50
R5
G10


51
R6
G1


52
R6
G2


53
R6
G3


54
R6
G4


55
R6
G5


56
R6
G6


57
R6
G7


58
R6
G8


59
R6
G9


60
R6
G10


61
R7
G1


62
R7
G2


63
R7
G3


64
R7
G4


65
R7
G5


66
R7
G6


67
R7
G7


68
R7
G8


69
R7
G9


70
R7
G10


71
R8
G1


72
R8
G2


73
R8
G3


74
R8
G4


75
R8
G5


76
R8
G6


77
R8
G7


78
R8
G8


79
R8
G9


80
R8
G10


81
R9
G1


82
R9
G2


83
R9
G3


84
R9
G4


85
R9
G5


86
R9
G6


87
R9
G7


88
R9
G8


89
R9
G9


90
R9
G10


91
R10
G1


92
R10
G2


93
R10
G3


94
R10
G4


95
R10
G5


96
R10
G6


97
R10
G7


98
R10
G8


99
R10
G9


100
R10
G10


101
R11
G1


102
R11
G2


103
R11
G3


104
R11
G4


105
R11
G5


106
R11
G6


107
R11
G7


108
R11
G8


109
R11
G9


110
R11
G10


111
R12
G1


112
R12
G2


113
R12
G3


114
R12
G4


115
R12
G5


116
R12
G6


117
R12
G7


118
R12
G8


119
R12
G9


120
R12
G10


121
R13
G1


122
R13
G2


123
R13
G3


124
R13
G4


125
R13
G5


126
R13
G6


127
R13
G7


128
R13
G8


129
R13
G9


130
R13
G10


131
R14
G1


132
R14
G2


133
R14
G3


134
R14
G4


135
R14
G5


136
R14
G6


137
R14
G7


138
R14
G8


139
R14
G9


140
R14
G10


141
R15
G1


142
R15
G2


143
R15
G3


144
R15
G4


145
R15
G5


146
R15
G6


147
R15
G7


148
R15
G8


149
R15
G9


150
R15
G10


151
R16
G1


152
R16
G2


153
R16
G3


154
R16
G4


155
R16
G5


156
R16
G6


157
R16
G7


158
R16
G8


159
R16
G9


160
R16
G10


161
R17
G1


162
R17
G2


163
R17
G3


164
R17
G4


165
R17
G5


166
R17
G6


167
R17
G7


168
R17
G8


169
R17
G9


170
R17
G10


171
R18
G1


172
R18
G2


173
R18
G3


174
R18
G4


175
R18
G5


176
R18
G6


177
R18
G7


178
R18
G8


179
R18
G9


180
R18
G10


181
R19
G1


182
R19
G2


183
R19
G3


184
R19
G4


185
R19
G5


186
R19
G6


187
R19
G7


188
R19
G8


189
R19
G9


190
R19
G10


191
R20
G1


192
R20
G2


193
R20
G3


194
R20
G4


195
R20
G5


196
R20
G6


197
R20
G7


198
R20
G8


199
R20
G9


200
R20
G10








LAi-10, where i=an integer from 201 to 240, that are based on a structure of Formula 10




where in each LA201-10 to LA240-10, R and RD have the following definitions for each i:













i
R
RD

















201
R1
H


202
R3
H


203
R5
H


204
R7
H


205
R9
H


206
R11
H


207
R13
H


208
R15
H


209
R17
H


210
R19
H


211
R1
CH3


212
R3
CH3


213
R5
CH3


214
R7
CH3


215
R9
CH3


216
R11
CH3


217
R13
CH3


218
R15
CH3


219
R17
CH3


220
R19
CH3


221
R2
H


222
R4
H


223
R6
H


224
R8
H


225
R10
H


226
R12
H


227
R14
H


228
R16
H


229
R18
H


230
R20
H


231
R2
CH3


232
R4
CH3


233
R6
CH3


234
R8
CH3


235
R10
CH3


236
R12
CH3


237
R14
CH3


238
R16
CH3


239
R18
CH3


240
R20
CH3








LAi-14, where i=an integer from 241 to 640, that are based on a structure of Formula 14




LAi-15, where i=an integer from 241 to 640, that are based on a structure of Formula 15




wherein in each LA241-14 to LA640-14, and LA241-14 to LA640-14, R, G, and R′ have the following definitions for each i:














i
R
G
R′


















241
R1
G1
CH3


242
R1
G2
CH3


243
R1
G3
CH3


244
R1
G4
CH3


245
R1
G5
CH3


246
R1
G6
CH3


247
R1
G7
CH3


248
R1
G8
CH3


249
R1
G9
CH3


250
R1
G10
CH3


251
R2
G1
CH3


252
R2
G2
CH3


253
R2
G3
CH3


254
R2
G4
CH3


255
R2
G5
CH3


256
R2
G6
CH3


257
R2
G7
CH3


258
R2
G8
CH3


259
R2
G9
CH3


260
R2
G10
CH3


261
R3
G1
CH3


262
R3
G2
CH3


263
R3
G3
CH3


264
R3
G4
CH3


265
R3
G5
CH3


266
R3
G6
CH3


267
R3
G7
CH3


268
R3
G8
CH3


269
R3
G9
CH3


270
R3
G10
CH3


271
R4
G1
CH3


272
R4
G2
CH3


273
R4
G3
CH3


274
R4
G4
CH3


275
R4
G5
CH3


276
R4
G6
CH3


277
R4
G7
CH3


278
R4
G8
CH3


279
R4
G9
CH3


280
R4
G10
CH3


281
R5
G1
CH3


282
R5
G2
CH3


283
R5
G3
CH3


284
R5
G4
CH3


285
R5
G5
CH3


286
R5
G6
CH3


287
R5
G7
CH3


288
R5
G8
CH3


289
R5
G9
CH3


290
R5
G10
CH3


291
R6
G1
CH3


292
R6
G2
CH3


293
R6
G3
CH3


294
R6
G4
CH3


295
R6
G5
CH3


296
R6
G6
CH3


297
R6
G7
CH3


298
R6
G8
CH3


299
R6
G9
CH3


300
R6
G10
CH3


301
R7
G1
CH3


302
R7
G2
CH3


303
R7
G3
CH3


304
R7
G4
CH3


305
R7
G5
CH3


306
R7
G6
CH3


307
R7
G7
CH3


308
R7
G8
CH3


309
R7
G9
CH3


310
R7
G10
CH3


311
R8
G1
CH3


312
R8
G2
CH3


313
R8
G3
CH3


314
R8
G4
CH3


315
R8
G5
CH3


316
R8
G6
CH3


317
R8
G7
CH3


318
R8
G8
CH3


319
R8
G9
CH3


320
R8
G10
CH3


321
R9
G1
CH3


322
R9
G2
CH3


323
R9
G3
CH3


324
R9
G4
CH3


325
R9
G5
CH3


326
R9
G6
CH3


327
R9
G7
CH3


328
R9
G8
CH3


329
R9
G9
CH3


330
R9
G10
CH3


331
R10
G1
CH3


332
R10
G2
CH3


333
R10
G3
CH3


334
R10
G4
CH3


335
R10
G5
CH3


336
R10
G6
CH3


337
R10
G7
CH3


338
R10
G8
CH3


339
R10
G9
CH3


340
R10
G10
CH3


341
R11
G1
CH3


342
R11
G2
CH3


343
R11
G3
CH3


344
R11
G4
CH3


345
R11
G5
CH3


346
R11
G6
CH3


347
R11
G7
CH3


348
R11
G8
CH3


349
R11
G9
CH3


350
R11
G10
CH3


351
R12
G1
CH3


352
R12
G2
CH3


353
R12
G3
CH3


354
R12
G4
CH3


355
R12
G5
CH3


356
R12
G6
CH3


357
R12
G7
CH3


358
R12
G8
CH3


359
R12
G9
CH3


360
R12
G10
CH3


361
R13
G1
CH3


362
R13
G2
CH3


363
R13
G3
CH3


364
R13
G4
CH3


365
R13
G5
CH3


366
R13
G6
CH3


367
R13
G7
CH3


368
R13
G8
CH3


369
R13
G9
CH3


370
R13
G10
CH3


371
R14
G1
CH3


372
R14
G2
CH3


373
R14
G3
CH3


374
R20
G10
CH(CH3)2


375
R14
G4
CH3


376
R14
G5
CH3


377
R14
G6
CH3


378
R14
G7
CH3


379
R14
G8
CH3


380
R14
G9
CH3


381
R14
G10
CH3


382
R15
G1
CH3


383
R15
G2
CH3


384
R15
G3
CH3


385
R15
G4
CH3


386
R15
G5
CH3


387
R15
G6
CH3


388
R15
G7
CH3


389
R15
G8
CH3


390
R15
G9
CH3


391
R15
G10
CH3


392
R16
G1
CH3


393
R16
G2
CH3


394
R16
G3
CH3


395
R16
G4
CH3


396
R16
G5
CH3


397
R16
G6
CH3


398
R16
G7
CH3


399
R16
G8
CH3


400
R16
G9
CH3


401
R16
G10
CH3


402
R17
G1
CH3


403
R17
G2
CH3


404
R17
G3
CH3


405
R17
G4
CH3


406
R17
G5
CH3


407
R17
G6
CH3


408
R17
G7
CH3


409
R17
G8
CH3


410
R17
G9
CH3


411
R17
G10
CH3


412
R18
G1
CH3


413
R18
G2
CH3


414
R18
G3
CH3


415
R18
G4
CH3


416
R18
G5
CH3


417
R18
G6
CH3


418
R18
G7
CH3


419
R18
G8
CH3


420
R18
G9
CH3


421
R18
G10
CH3


422
R19
G1
CH3


423
R19
G2
CH3


424
R19
G3
CH3


425
R19
G4
CH3


426
R19
G5
CH3


427
R19
G6
CH3


428
R19
G7
CH3


429
R19
G8
CH3


430
R19
G9
CH3


431
R19
G10
CH3


432
R20
G1
CH3


433
R20
G2
CH3


434
R20
G3
CH3


435
R20
G4
CH3


436
R20
G5
CH3


437
R20
G6
CH3


438
R20
G7
CH3


439
R20
G8
CH3


440
R20
G9
CH3


441
R20
G10
CH3


442
R1
G1
CH(CH3)2


443
R1
G2
CH(CH3)2


444
R1
G3
CH(CH3)2


445
R1
G4
CH(CH3)2


446
R1
G5
CH(CH3)2


447
R1
G6
CH(CH3)2


448
R1
G7
CH(CH3)2


449
R1
G8
CH(CH3)2


450
R1
G9
CH(CH3)2


451
R1
G10
CH(CH3)2


452
R2
G1
CH(CH3)2


453
R2
G2
CH(CH3)2


454
R2
G3
CH(CH3)2


455
R2
G4
CH(CH3)2


456
R2
G5
CH(CH3)2


457
R2
G6
CH(CH3)2


458
R2
G7
CH(CH3)2


459
R2
G8
CH(CH3)2


460
R2
G9
CH(CH3)2


461
R2
G10
CH(CH3)2


462
R3
G1
CH(CH3)2


463
R3
G2
CH(CH3)2


464
R3
G3
CH(CH3)2


465
R3
G4
CH(CH3)2


466
R3
G5
CH(CH3)2


467
R3
G6
CH(CH3)2


468
R3
G7
CH(CH3)2


469
R3
G8
CH(CH3)2


470
R3
G9
CH(CH3)2


471
R3
G10
CH(CH3)2


472
R4
G1
CH(CH3)2


473
R4
G2
CH(CH3)2


474
R4
G3
CH(CH3)2


475
R4
G4
CH(CH3)2


476
R4
G5
CH(CH3)2


477
R4
G6
CH(CH3)2


478
R4
G7
CH(CH3)2


479
R4
G8
CH(CH3)2


480
R4
G9
CH(CH3)2


481
R4
G10
CH(CH3)2


482
R5
G1
CH(CH3)2


483
R5
G2
CH(CH3)2


484
R5
G3
CH(CH3)2


485
R5
G4
CH(CH3)2


486
R5
G5
CH(CH3)2


487
R5
G6
CH(CH3)2


488
R5
G7
CH(CH3)2


489
R5
G8
CH(CH3)2


490
R5
G9
CH(CH3)2


491
R5
G10
CH(CH3)2


492
R6
G1
CH(CH3)2


493
R6
G2
CH(CH3)2


494
R6
G3
CH(CH3)2


495
R6
G4
CH(CH3)2


496
R6
G5
CH(CH3)2


497
R6
G6
CH(CH3)2


498
R6
G7
CH(CH3)2


499
R6
G8
CH(CH3)2


500
R6
G9
CH(CH3)2


501
R6
G10
CH(CH3)2


502
R7
G1
CH(CH3)2


503
R7
G2
CH(CH3)2


504
R7
G3
CH(CH3)2


505
R7
G4
CH(CH3)2


506
R7
G5
CH(CH3)2


507
R7
G6
CH(CH3)2


508
R7
G7
CH(CH3)2


509
R7
G8
CH(CH3)2


510
R7
G9
CH(CH3)2


511
R7
G10
CH(CH3)2


512
R8
G1
CH(CH3)2


513
R8
G2
CH(CH3)2


514
R8
G3
CH(CH3)2


515
R8
G4
CH(CH3)2


516
R8
G5
CH(CH3)2


517
R8
G6
CH(CH3)2


518
R8
G7
CH(CH3)2


519
R8
G8
CH(CH3)2


520
R8
G9
CH(CH3)2


521
R8
G10
CH(CH3)2


522
R9
G1
CH(CH3)2


523
R9
G2
CH(CH3)2


524
R9
G3
CH(CH3)2


525
R9
G4
CH(CH3)2


526
R9
G5
CH(CH3)2


527
R9
G6
CH(CH3)2


528
R9
G7
CH(CH3)2


529
R9
G8
CH(CH3)2


530
R9
G9
CH(CH3)2


531
R9
G10
CH(CH3)2


532
R10
G1
CH(CH3)2


533
R10
G2
CH(CH3)2


534
R10
G3
CH(CH3)2


535
R10
G4
CH(CH3)2


536
R10
G5
CH(CH3)2


537
R10
G6
CH(CH3)2


538
R10
G7
CH(CH3)2


539
R10
G8
CH(CH3)2


540
R10
G9
CH(CH3)2


541
R10
G10
CH(CH3)2


542
R11
G1
CH(CH3)2


543
R11
G2
CH(CH3)2


544
R11
G3
CH(CH3)2


545
R11
G4
CH(CH3)2


546
R11
G5
CH(CH3)2


547
R11
G6
CH(CH3)2


548
R11
G7
CH(CH3)2


549
R11
G8
CH(CH3)2


550
R11
G9
CH(CH3)2


551
R11
G10
CH(CH3)2


552
R12
G1
CH(CH3)2


553
R12
G2
CH(CH3)2


554
R12
G3
CH(CH3)2


555
R12
G4
CH(CH3)2


556
R12
G5
CH(CH3)2


557
R12
G6
CH(CH3)2


558
R12
G7
CH(CH3)2


559
R12
G8
CH(CH3)2


560
R12
G9
CH(CH3)2


561
R12
G10
CH(CH3)2


562
R13
G1
CH(CH3)2


563
R13
G2
CH(CH3)2


564
R13
G3
CH(CH3)2


565
R13
G4
CH(CH3)2


566
R13
G5
CH(CH3)2


567
R13
G6
CH(CH3)2


568
R13
G7
CH(CH3)2


569
R13
G8
CH(CH3)2


570
R13
G9
CH(CH3)2


571
R13
G10
CH(CH3)2


572
R14
G1
CH(CH3)2


573
R14
G2
CH(CH3)2


574
R14
G3
CH(CH3)2


575
R14
G4
CH(CH3)2


576
R14
G5
CH(CH3)2


577
R14
G6
CH(CH3)2


578
R14
G7
CH(CH3)2


579
R14
G8
CH(CH3)2


580
R14
G9
CH(CH3)2


581
R14
G10
CH(CH3)2


582
R15
G1
CH(CH3)2


583
R15
G2
CH(CH3)2


584
R15
G3
CH(CH3)2


585
R15
G4
CH(CH3)2


586
R15
G5
CH(CH3)2


587
R15
G6
CH(CH3)2


588
R15
G7
CH(CH3)2


589
R15
G8
CH(CH3)2


590
R15
G9
CH(CH3)2


591
R15
G10
CH(CH3)2


592
R16
G1
CH(CH3)2


593
R16
G2
CH(CH3)2


594
R16
G3
CH(CH3)2


595
R16
G4
CH(CH3)2


596
R16
G5
CH(CH3)2


597
R16
G6
CH(CH3)2


598
R16
G7
CH(CH3)2


599
R16
G8
CH(CH3)2


600
R16
G9
CH(CH3)2


601
R16
G10
CH(CH3)2


602
R17
G1
CH(CH3)2


603
R17
G2
CH(CH3)2


604
R17
G3
CH(CH3)2


605
R17
G4
CH(CH3)2


606
R17
G5
CH(CH3)2


607
R17
G6
CH(CH3)2


608
R17
G7
CH(CH3)2


609
R17
G8
CH(CH3)2


610
R17
G9
CH(CH3)2


611
R17
G10
CH(CH3)2


612
R18
G1
CH(CH3)2


613
R18
G2
CH(CH3)2


614
R18
G3
CH(CH3)2


615
R18
G4
CH(CH3)2


616
R18
G5
CH(CH3)2


617
R18
G6
CH(CH3)2


618
R18
G7
CH(CH3)2


619
R18
G8
CH(CH3)2


620
R18
G9
CH(CH3)2


621
R18
G10
CH(CH3)2


622
R19
G1
CH(CH3)2


623
R19
G2
CH(CH3)2


624
R19
G3
CH(CH3)2


625
R19
G4
CH(CH3)2


626
R19
G5
CH(CH3)2


627
R19
G6
CH(CH3)2


628
R19
G7
CH(CH3)2


629
R19
G8
CH(CH3)2


630
R19
G9
CH(CH3)2


631
R19
G10
CH(CH3)2


632
R20
G1
CH(CH3)2


633
R20
G2
CH(CH3)2


634
R20
G3
CH(CH3)2


635
R20
G4
CH(CH3)2


636
R20
G5
CH(CH3)2


637
R20
G6
CH(CH3)2


638
R20
G7
CH(CH3)2


639
R20
G8
CH(CH3)2


640
R20
G9
CH(CH3)2








wherein R1 to R20 have the following structures:







wherein G1 to G10 have the following structures

13. The compound of claim 1, wherein the compound has a formula of M(LA)x(LB)y(LC)z wherein LB and LC are each a bidentate ligand; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M.

14. The compound of claim 13, wherein LB and LC are each independently selected from the group consisting of:









each Y1 to Y13 is independently selected from the group consisting of carbon and nitrogen;
Y′ is selected from the group consisting of B Re, N Re, P Re, O, S, Se, C═O, S═O, SO2, CReRf, SiReRf, and GeReRf;
Re and Rf can be fused or joined to form a ring;
each Ra, Rb, Rc, and Rd independently represents from mono substitution to the maximum possible number of substitutions, or no substitution;
each Ra, Rb, Rc, Rd, Re and Rf is independently a hydroge or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and
any two adjacent substituents of Ra, Rb, Rc, and Rd can be fused or joined to form a ring or form a multidentate ligand.

15. The compound of claim 13, wherein the compound is Compound Ax-F having the formula Ir(LAi-f)3, Compound By-F having the formula Ir(LAi-f)(LBk)2, or Compound Cz-F having the formula Ir(LAi-f)2(LCj);
wherein x=i, F=f, y=263i+k−263, and z=768i+j−768;
wherein i is an integer from 1 to 640,f is an integer from 1 to 15, and k is an integer from 1 to 263, and j is an integer from 1 to 768;
wherein LBk have the following structures:





































































































































































and
LCj has the structure of LCj-1, having the structures based on a structure of or





or LCj-II,
having the structures based on a structure of





wherein for each LCj in LCj-I and LCj-II,
R1 and R2 are defined as provided below:
















LCj
R1
R2









LC1
RD1
RD1



LC2
RD2
RD2



LC3
RD3
RD3



LC4
RD4
RD4



LC5
RD5
RD5



LC6
RD6
RD6



LC7
RD7
RD7



LC8
RD8
RD8



LC9
RD9
RD9



LC10
RD10
RD10



LC11
RD11
RD11



LC12
RD12
RD12



LC13
RD13
RD13



LC14
RD14
RD14



LC15
RD15
RD15



LC16
RD16
RD16



LC17
RD17
RD17



LC18
RD18
RD18



LC19
RD19
RD19



LC20
RD20
RD20



LC21
RD21
RD21



LC22
RD22
RD22



LC23
RD23
RD23



LC24
RD24
RD24



LC25
RD25
RD25



LC26
RD26
RD26



LC27
RD27
RD27



LC28
RD28
RD28



LC29
RD29
RD29



LC30
RD30
RD30



LC31
RD31
RD31



LC32
RD32
RD32



LC33
RD33
RD33



LC34
RD34
RD34



LC35
RD35
RD35



LC36
RD36
RD36



LC37
RD37
RD37



LC38
RD38
RD38



LC39
RD39
RD39



LC40
RD40
RD40



LC41
RD41
RD41



LC42
RD42
RD42



LC43
RD43
RD43



LC44
RD44
RD44



LC45
RD45
RD45



LC46
RD46
RD46



LC47
RD47
RD47



LC48
RD48
RD48



LC49
RD49
RD49



LC50
RD50
RD50



LC51
RD51
RD51



LC52
RD52
RD52



LC53
RD53
RD53



LC54
RD54
RD54



LC55
RD55
RD55



LC56
RD56
RD56



LC57
RD57
RD57



LC58
RD58
RD58



LC59
RD59
RD59



LC60
RD60
RD60



LC61
RD61
RD61



LC62
RD62
RD62



LC63
RD63
RD63



LC64
RD64
RD64



LC65
RD65
RD65



LC66
RD66
RD66



LC67
RD67
RD67



LC68
RD68
RD68



LC69
RD69
RD69



LC70
RD70
RD70



LC71
RD71
RD71



LC72
RD72
RD72



LC73
RD73
RD73



LC74
RD74
RD74



LC75
RD75
RD75



LC76
RD76
RD76



LC77
RD77
RD77



LC78
RD78
RD78



LC79
RD79
RD79



LC80
RD80
RD80



LC81
RD81
RD81



LC82
RD82
RD82



LC83
RD83
RD83



LC84
RD84
RD84



LC85
RD85
RD85



LC86
RD86
RD86



LC87
RD87
RD87



LC88
RD88
RD88



LC89
RD89
RD89



LC90
RD90
RD90



LC91
RD91
RD91



LC92
RD92
RD92



LC93
RD93
RD93



LC94
RD94
RD94



LC95
RD95
RD95



LC96
RD96
RD96



LC97
RD97
RD97



LC98
RD98
RD98



LC99
RD99
RD99



LC100
RD100
RD100



LC101
RD101
RD101



LC102
RD102
RD102



LC103
RD103
RD103



LC104
RD104
RD104



LC105
RD105
RD105



LC106
RD106
RD106



LC107
RD107
RD107



LC108
RD108
RD108



LC109
RD109
RD109



LC110
RD110
RD110



LC111
RD111
RD111



LC112
RD112
RD112



LC113
RD113
RD113



LC114
RD114
RD114



LC115
RD115
RD115



LC116
RD116
RD116



LC117
RD117
RD117



LC118
RD118
RD118



LC119
RD119
RD119



LC120
RD120
RD120



LC121
RD121
RD121



LC122
RD122
RD122



LC123
RD123
RD123



LC124
RD124
RD124



LC125
RD125
RD125



LC126
RD126
RD126



LC127
RD127
RD127



LC128
RD128
RD128



LC129
RD129
RD129



LC130
RD130
RD130



LC131
RD131
RD131



LC132
RD132
RD132



LC133
RD133
RD133



LC134
RD134
RD134



LC135
RD135
RD135



LC136
RD136
RD136



LC137
RD137
RD137



LC138
RD138
RD138



LC139
RD139
RD139



LC140
RD140
RD140



LC141
RD141
RD141



LC142
RD142
RD142



LC143
RD143
RD143



LC144
RD144
RD144



LC145
RD145
RD145



LC146
RD146
RD146



LC147
RD147
RD147



LC148
RD148
RD148



LC149
RD149
RD149



LC150
RD150
RD150



LC151
RD151
RD151



LC152
RD152
RD152



LC153
RD153
RD153



LC154
RD154
RD154



LC155
RD155
RD155



LC156
RD156
RD156



LC157
RD157
RD157



LC158
RD158
RD158



LC159
RD159
RD159



LC160
RD160
RD160



LC161
RD161
RD161



LC162
RD162
RD162



LC163
RD163
RD163



LC164
RD164
RD164



LC165
RD165
RD165



LC166
RD166
RD166



LC167
RD167
RD167



LC168
RD168
RD168



LC169
RD169
RD169



LC170
RD170
RD170



LC171
RD171
RD171



LC172
RD172
RD172



LC173
RD173
RD173



LC174
RD174
RD174



LC175
RD175
RD175



LC176
RD176
RD176



LC177
RD177
RD177



LC178
RD178
RD178



LC179
RD179
RD179



LC180
RD180
RD180



LC181
RD181
RD181



LC182
RD182
RD182



LC183
RD183
RD183



LC184
RD184
RD184



LC185
RD185
RD185



LC186
RD186
RD186



LC187
RD187
RD187



LC188
RD188
RD188



LC189
RD189
RD189



LC190
RD190
RD190



LC191
RD191
RD191



LC192
RD192
RD192



LC193
RD1
RD3



LC194
RD1
RD4



LC195
RD1
RD5



LC196
RD1
RD9



LC197
RD1
RD10



LC198
RD1
RD17



LC199
RD1
RD18



LC200
RD1
RD20



LC201
RD1
RD22



LC202
RD1
RD37



LC203
RD1
RD40



LC204
RD1
RD41



LC205
RD1
RD42



LC206
RD1
RD43



LC207
RD1
RD48



LC208
RD1
RD49



LC209
RD1
RD50



LC210
RD1
RD54



LC211
RD1
RD55



LC212
RD1
RD58



LC213
RD1
RD59



LC214
RD1
RD78



LC215
RD1
RD79



LC216
RD1
RD81



LC217
RD1
RD87



LC218
RD1
RD88



LC219
RD1
RD89



LC220
RD1
RD93



LC221
RD1
RD116



LC222
RD1
RD117



LC223
RD1
RD118



LC224
RD1
RD119



LC225
RD1
RD120



LC226
RD1
RD133



LC227
RD1
RD134



LC228
RD1
RD135



LC229
RD1
RD136



LC230
RD1
RD143



LC231
RD1
RD144



LC232
RD1
RD145



LC233
RD1
RD146



LC234
RD1
RD147



LC235
RD1
RD149



LC236
RD1
RD151



LC237
RD1
RD154



LC238
RD1
RD155



LC239
RD1
RD161



LC240
RD1
RD175



LC241
RD4
RD3



LC242
RD4
RD5



LC243
RD4
RD9



LC244
RD4
RD10



LC245
RD4
RD17



LC246
RD4
RD18



LC247
RD4
RD20



LC248
RD4
RD22



LC249
RD4
RD37



LC250
RD4
RD40



LC251
RD4
RD41



LC252
RD4
RD42



LC253
RD4
RD43



LC254
RD4
RD48



LC255
RD4
RD49



LC256
RD4
RD50



LC257
RD4
RD54



LC258
RD4
RD55



LC259
RD4
RD58



LC260
RD4
RD59



LC261
RD4
RD78



LC262
RD4
RD79



LC263
RD4
RD81



LC264
RD4
RD87



LC265
RD4
RD88



LC266
RD4
RD89



LC267
RD4
RD93



LC268
RD4
RD116



LC269
RD4
RD117



LC270
RD4
RD118



LC271
RD4
RD119



LC272
RD4
RD120



LC273
RD4
RD133



LC274
RD4
RD134



LC275
RD4
RD135



LC276
RD4
RD136



LC277
RD4
RD143



LC278
RD4
RD144



LC279
RD4
RD145



LC280
RD4
RD146



LC281
RD4
RD147



LC282
RD4
RD149



LC283
RD4
RD151



LC284
RD4
RD154



LC285
RD4
RD155



LC286
RD4
RD161



LC287
RD4
RD175



LC288
RD9
RD3



LC289
RD9
RD5



LC290
RD9
RD10



LC291
RD9
RD17



LC292
RD9
RD18



LC293
RD9
RD20



LC294
RD9
RD22



LC295
RD9
RD37



LC296
RD9
RD40



LC297
RD9
RD41



LC298
RD9
RD42



LC299
RD9
RD43



LC300
RD9
RD48



LC301
RD9
RD49



LC302
RD9
RD50



LC303
RD9
RD54



LC304
RD9
RD55



LC305
RD9
RD58



LC306
RD9
RD59



LC307
RD9
RD78



LC308
RD9
RD79



LC309
RD9
RD81



LC310
RD9
RD87



LC311
RD9
RD88



LC312
RD9
RD89



LC313
RD9
RD93



LC314
RD9
RD116



LC315
RD9
RD117



LC316
RD9
RD118



LC317
RD9
RD119



LC318
RD9
RD120



LC319
RD9
RD133



LC320
RD9
RD134



LC321
RD9
RD135



LC322
RD9
RD136



LC323
RD9
RD143



LC324
RD9
RD144



LC325
RD9
RD145



LC326
RD9
RD146



LC327
RD9
RD147



LC328
RD9
RD149



LC329
RD9
RD151



LC330
RD9
RD154



LC331
RD9
RD155



LC332
RD9
RD161



LC333
RD9
RD175



LC334
RD10
RD3



LC335
RD10
RD5



LC336
RD10
RD17



LC337
RD10
RD18



LC338
RD10
RD20



LC339
RD10
RD22



LC340
RD10
RD37



LC341
RD10
RD40



LC342
RD10
RD41



LC343
RD10
RD42



LC344
RD10
RD43



LC345
RD10
RD48



LC346
RD10
RD49



LC347
RD10
RD50



LC348
RD10
RD54



LC349
RD10
RD55



LC350
RD10
RD58



LC351
RD10
RD59



LC352
RD10
RD78



LC353
RD10
RD79



LC354
RD10
RD81



LC355
RD10
RD87



LC356
RD10
RD88



LC357
RD10
RD89



LC358
RD10
RD93



LC359
RD10
RD116



LC360
RD10
RD117



LC361
RD10
RD118



LC362
RD10
RD119



LC363
RD10
RD120



LC364
RD10
RD133



LC365
RD10
RD134



LC366
RD10
RD135



LC367
RD10
RD136



LC368
RD10
RD143



LC369
RD10
RD144



LC370
RD10
RD145



LC371
RD10
RD146



LC372
RD10
RD147



LC373
RD10
RD149



LC374
RD10
RD151



LC375
RD10
RD154



LC376
RD10
RD155



LC377
RD10
RD161



LC378
RD10
RD175



LC379
RD17
RD3



LC380
RD17
RD5



LC381
RD17
RD18



LC382
RD17
RD20



LC383
RD17
RD22



LC384
RD17
RD37



LC385
RD17
RD40



LC386
RD17
RD41



LC387
RD17
RD42



LC388
RD17
RD43



LC389
RD17
RD48



LC390
RD17
RD49



LC391
RD17
RD50



LC392
RD17
RD54



LC393
RD17
RD55



LC394
RD17
RD58



LC395
RD17
RD59



LC396
RD17
RD78



LC397
RD17
RD79



LC398
RD17
RD81



LC399
RD17
RD87



LC400
RD17
RD88



LC401
RD17
RD89



LC402
RD17
RD93



LC403
RD17
RD116



LC404
RD17
RD117



LC405
RD17
RD118



LC406
RD17
RD119



LC407
RD17
RD120



LC408
RD17
RD133



LC409
RD17
RD134



LC410
RD17
RD135



LC411
RD17
RD136



LC412
RD17
RD143



LC413
RD17
RD144



LC414
RD17
RD145



LC415
RD17
RD146



LC416
RD17
RD147



LC417
RD17
RD149



LC418
RD17
RD151



LC419
RD17
RD154



LC420
RD17
RD155



LC421
RD17
RD161



LC422
RD17
RD175



LC423
RD50
RD3



LC424
RD50
RD5



LC425
RD50
RD18



LC426
RD50
RD20



LC427
RD50
RD22



LC428
RD50
RD37



LC429
RD50
RD40



LC430
RD50
RD41



LC431
RD50
RD42



LC432
RD50
RD43



LC433
RD50
RD48



LC434
RD50
RD49



LC435
RD50
RD54



LC436
RD50
RD55



LC437
RD50
RD58



LC438
RD50
RD59



LC439
RD50
RD78



LC440
RD50
RD79



LC441
RD50
RD81



LC442
RD50
RD87



LC443
RD50
RD88



LC444
RD50
RD89



LC445
RD50
RD93



LC446
RD50
RD116



LC447
RD50
RD117



LC448
RD50
RD118



LC449
RD50
RD119



LC450
RD50
RD120



LC451
RD50
RD133



LC452
RD50
RD134



LC453
RD50
RD135



LC454
RD50
RD136



LC455
RD50
RD143



LC456
RD50
RD144



LC457
RD50
RD145



LC458
RD50
RD146



LC459
RD50
RD147



LC460
RD50
RD149



LC461
RD50
RD151



LC462
RD50
RD154



LC463
RD50
RD155



LC464
RD50
RD161



LC465
RD50
RD175



LC466
RD55
RD3



LC467
RD55
RD5



LC468
RD55
RD18



LC469
RD55
RD20



LC470
RD55
RD22



LC471
RD55
RD37



LC472
RD55
RD40



LC473
RD55
RD41



LC474
RD55
RD42



LC475
RD55
RD43



LC476
RD55
RD48



LC477
RD55
RD49



LC478
RD55
RD54



LC479
RD55
RD58



LC480
RD55
RD59



LC481
RD55
RD78



LC482
RD55
RD79



LC483
RD55
RD81



LC484
RD55
RD87



LC485
RD55
RD88



LC486
RD55
RD89



LC487
RD55
RD93



LC488
RD55
RD116



LC489
RD55
RD117



LC490
RD55
RD118



LC491
RD55
RD119



LC492
RD55
RD120



LC493
RD55
RD133



LC494
RD55
RD134



LC495
RD55
RD135



LC496
RD55
RD136



LC497
RD55
RD143



LC498
RD55
RD144



LC499
RD55
RD145



LC500
RD55
RD146



LC501
RD55
RD147



LC502
RD55
RD149



LC503
RD55
RD151



LC504
RD55
RD154



LC505
RD55
RD155



LC506
RD55
RD161



LC507
RD55
RD175



LC508
RD116
RD3



LC509
RD116
RD5



LC510
RD116
RD17



LC511
RD116
RD18



LC512
RD116
RD20



LC513
RD116
RD22



LC514
RD116
RD37



LC515
RD116
RD40



LC516
RD116
RD41



LC517
RD116
RD42



LC518
RD116
RD43



LC519
RD116
RD48



LC520
RD116
RD49



LC521
RD116
RD54



LC522
RD116
RD58



LC523
RD116
RD59



LC524
RD116
RD78



LC525
RD116
RD79



LC526
RD116
RD81



LC527
RD116
RD87



LC528
RD116
RD88



LC529
RD116
RD89



LC530
RD116
RD93



LC531
RD116
RD117



LC532
RD116
RD118



LC533
RD116
RD119



LC534
RD116
RD120



LC535
RD116
RD133



LC536
RD116
RD134



LC537
RD116
RD135



LC538
RD116
RD136



LC539
RD116
RD143



LC540
RD116
RD144



LC541
RD116
RD145



LC542
RD116
RD146



LC543
RD116
RD147



LC544
RD116
RD149



LC545
RD116
RD151



LC546
RD116
RD154



LC547
RD116
RD155



LC548
RD116
RD161



LC549
RD116
RD175



LC550
RD143
RD3



LC551
RD143
RD5



LC552
RD143
RD17



LC553
RD143
RD18



LC554
RD143
RD20



LC555
RD143
RD22



LC556
RD143
RD37



LC557
RD143
RD40



LC558
RD143
RD41



LC559
RD143
RD42



LC560
RD143
RD43



LC561
RD143
RD48



LC562
RD143
RD49



LC563
RD143
RD54



LC564
RD143
RD58



LC565
RD143
RD59



LC566
RD143
RD78



LC567
RD143
RD79



LC568
RD143
RD81



LC569
RD143
RD87



LC570
RD143
RD88



LC571
RD143
RD89



LC572
RD143
RD93



LC573
RD143
RD116



LC574
RD143
RD117



LC575
RD143
RD118



LC576
RD143
RD119



LC577
RD143
RD120



LC578
RD143
RD133



LC579
RD143
RD134



LC580
RD143
RD135



LC581
RD143
RD136



LC582
RD143
RD144



LC583
RD143
RD145



LC584
RD143
RD146



LC585
RD143
RD147



LC586
RD143
RD149



LC587
RD143
RD151



LC588
RD143
RD154



LC589
RD143
RD155



LC590
RD143
RD161



LC591
RD143
RD175



LC592
RD144
RD3



LC593
RD144
RD5



LC594
RD144
RD17



LC595
RD144
RD18



LC596
RD144
RD20



LC597
RD144
RD22



LC598
RD144
RD37



LC599
RD144
RD40



LC600
RD144
RD41



LC601
RD144
RD42



LC602
RD144
RD43



LC603
RD144
RD48



LC604
RD144
RD49



LC605
RD144
RD54



LC606
RD144
RD58



LC607
RD144
RD59



LC608
RD144
RD78



LC609
RD144
RD79



LC610
RD144
RD81



LC611
RD144
RD87



LC612
RD144
RD88



LC613
RD144
RD89



LC614
RD144
RD93



LC615
RD144
RD116



LC616
RD144
RD117



LC617
RD144
RD118



LC618
RD144
RD119



LC619
RD144
RD120



LC620
RD144
RD133



LC621
RD144
RD134



LC622
RD144
RD135



LC623
RD144
RD136



LC624
RD144
RD145



LC625
RD144
RD146



LC626
RD144
RD147



LC627
RD144
RD149



LC628
RD144
RD151



LC629
RD144
RD154



LC630
RD144
RD155



LC631
RD144
RD161



LC632
RD144
RD175



LC633
RD145
RD3



LC634
RD145
RD5



LC635
RD145
RD17



LC636
RD145
RD18



LC637
RD145
RD20



LC638
RD145
RD22



LC639
RD145
RD37



LC640
RD145
RD40



LC641
RD145
RD41



LC642
RD145
RD42



LC643
RD145
RD43



LC644
RD145
RD48



LC645
RD145
RD49



LC646
RD145
RD54



LC647
RD145
RD58



LC648
RD145
RD59



LC649
RD145
RD78



LC650
RD145
RD79



LC651
RD145
RD81



LC652
RD145
RD87



LC653
RD145
RD88



LC654
RD145
RD89



LC655
RD145
RD93



LC656
RD145
RD116



LC657
RD145
RD117



LC658
RD145
RD118



LC659
RD145
RD119



LC660
RD145
RD120



LC661
RD145
RD133



LC662
RD145
RD134



LC663
RD145
RD135



LC664
RD145
RD136



LC665
RD145
RD146



LC666
RD145
RD147



LC667
RD145
RD149



LC668
RD145
RD151



LC669
RD145
RD154



LC670
RD145
RD155



LC671
RD145
RD161



LC672
RD145
RD175



LC673
RD146
RD3



LC674
RD146
RD5



LC675
RD146
RD17



LC676
RD146
RD18



LC677
RD146
RD20



LC678
RD146
RD22



LC679
RD146
RD37



LC680
RD146
RD40



LC681
RD146
RD41



LC682
RD146
RD42



LC683
RD146
RD43



LC684
RD146
RD48



LC685
RD146
RD49



LC686
RD146
RD54



LC687
RD146
RD58



LC688
RD146
RD59



LC689
RD146
RD78



LC690
RD146
RD79



LC691
RD146
RD81



LC692
RD146
RD87



LC693
RD146
RD88



LC694
RD146
RD89



LC695
RD146
RD93



LC696
RD146
RD117



LC697
RD146
RD118



LC698
RD146
RD119



LC699
RD146
RD120



LC700
RD146
RD133



LC701
RD146
RD134



LC702
RD146
RD135



LC703
RD146
RD136



LC704
RD146
RD146



LC705
RD146
RD147



LC706
RD146
RD149



LC707
RD146
RD151



LC708
RD146
RD154



LC709
RD146
RD155



LC710
RD146
RD161



LC711
RD146
RD175



LC712
RD133
RD3



LC713
RD133
RD5



LC714
RD133
RD3



LC715
RD133
RD18



LC716
RD133
RD20



LC717
RD133
RD22



LC718
RD133
RD37



LC719
RD133
RD40



LC720
RD133
RD41



LC721
RD133
RD42



LC722
RD133
RD43



LC723
RD133
RD48



LC724
RD133
RD49



LC725
RD133
RD54



LC726
RD133
RD58



LC727
RD133
RD59



LC728
RD133
RD78



LC729
RD133
RD79



LC730
RD133
RD81



LC731
RD133
RD87



LC732
RD133
RD88



LC733
RD133
RD89



LC734
RD133
RD93



LC735
RD133
RD117



LC736
RD133
RD118



LC737
RD133
RD119



LC738
RD133
RD120



LC739
RD133
RD133



LC740
RD133
RD134



LC741
RD133
RD135



LC742
RD133
RD136



LC743
RD133
RD146



LC744
RD133
RD147



LC745
RD133
RD149



LC746
RD133
RD151



LC747
RD133
RD154



LC748
RD133
RD155



LC749
RD133
RD161



LC750
RD133
RD175



LC751
RD175
RD3



LC752
RD175
RD5



LC753
RD175
RD18



LC754
RD175
RD20



LC755
RD175
RD22



LC756
RD175
RD37



LC757
RD175
RD40



LC758
RD175
RD41



LC759
RD175
RD42



LC760
RD175
RD43



LC761
RD175
RD48



LC762
RD175
RD49



LC763
RD175
RD54



LC764
RD175
RD58



LC765
RD175
RD59



LC766
RD175
RD78



LC767
RD175
RD79



LC768
RD175
RD81









wherein RD1 to RD192 have the following structures:

16. An organic light emitting device (OLED) comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand LA of Formula I




wherein,
T is a fused ring system that comprises a structure of Formula II




ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
Z is C or N;
RB represents mono to the maximum number of allowable substitutions, or no substitution;
X1 to X6 are each C or N;
each R, RA, and RB is independently a 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;
when ring A bonds to X3 or X4, at least one of the following is true:
at least one of X1-X6 is N;
Z is C;
R is a hydrogen or a substituent selected from the group consisting of deuterium, halogen, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;

LA is complexed to a metal M to form a 5-membered chelate ring;
M can be coordinated to other ligands; and
the ligand LA can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate,
or hexadentate ligand; and
any two substituents can be joined or fused together to form a ring.

17. The OLED of claim 16, wherein the organic layer further comprises a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

18. The OLED of claim 16, wherein the host is selected from the group consisting of:













and combinations thereof.

19. A consumer product comprising an organic light-emitting device (OLED) comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand LA of Formula I




wherein,
T is a fused ring system that comprises a structure of Formula II




ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
Z is C or N;
RB represents mono to the maximum number of allowable substitutions, or no substitution;
X1 to X6 are each C or N;
each R, RA, and RB is independently a 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;
when ring A bonds to X3 or X4, at least one of the following is true:
at least one of X1-X6 is N,
Z is C;
R is a hydrogen or a substituent selected from the group consisting of deuterium, halogen, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;

LA is complexed to a metal M to form a 5-membered chelate ring;
M can be coordinated to other ligands; and
the ligand LA can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate,
or hexadentate ligand; and
any two substituents can be joined or fused together to form a ring.

20. A formulation comprising a compound of claim 1.