Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. A compound of formula Ir (LA) x (LB) y (LC) z is provided, wherein LA comprises the structure of formula I: # imgabs0 # and each of LB and LC is a different bidentate ligand. In said compounds of formula Ir (LA) x (LB) y (LC) z wherein Part A is a polycyclic fused ring system comprising at least three rings, including at least one non-benzene ring; part B is a monocyclic or polycyclic fused ring system; each of X1, X2 and Z1 is C or N; the Ir-C1 bond is a metal-carbene bond; y'is a linking group; l1 is a direct bond or a linking group; k1 is a direct bond or a linking group; and each RA and RB is hydrogen or a universal substituent as defined herein. Formulations, OLEDs, and consumer products containing the compounds are also provided.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 632,362, filed Apr. 10, 2024; U.S. Provisional Application No. 63 / 619,914, filed Jan. 11, 2024; U.S. Provisional Application No. 63 / 619,527, filed Jan. 10, 2024; U.S. Provisional Application No. 63 / 618,688, filed Jan. 8, 2024; U.S. Provisional Application No. 63 / 614,848, filed Dec. 26, 2023; and U.S. Provisional Application No. 63 / 609,906, filed Dec. 14, 2023, under 35 U.S.C. § 119(e), the entire content of which is incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure generally relates to organic or metal coordination compounds and formulations and their various uses, including as emitters, sensitizers, charge transporters, or exciton transporters in devices such as organic light-emitting diodes and related electronic devices and consumer products. BACKGROUND OF THE INVENTION

[0004] For various reasons, optoelectronic devices that utilize organic materials have become increasingly popular. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for a cost advantage over inorganic devices. Additionally, the inherent properties of organic materials, such as their flexibility, can make them more suitable for certain applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

[0005] OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly attractive technology for applications such as flat panel displays, lighting, and backlighting.

[0006] One application of phosphorescent emissive molecules is full-color displays. Industry standards for such displays require pixels that are suitable for emitting specific colors (referred to as “saturated” colors). Specifically, these standards require saturated red, green, and blue pixels. Alternatively, an OLED can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emissions. The same technique can be used for OLEDs. White OLEDs can be single-emitting layer (EML) devices or stacked structures. Color can be measured using CIE coordinates well known in the art. SUMMARY OF THE INVENTION

[0007] In one aspect, the present disclosure provides a compound comprising a structure of Ir(L A ) x (L B ) y (L C ) z , wherein the first ligand L A comprises a structure of Formula I, and each of the ligands L B and L C is independently a bidentate ligand, wherein the ligands L B and L C are different. In the compound of Ir(L A ) x (L B ) y (L C ) z :

[0008] x is 1, 2 or 3;

[0009] y and z are each independently 0, 1 or 2;

[0010] x + y + z = 3;

[0011] Moiety A is a polycyclic fused-ring system comprising at least three rings, wherein each ring of the polycyclic fused-ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0012] Moiety A comprises at least one non-benzenoid ring;

[0013] Moiety B is a monocyclic or polycyclic fused-ring system, wherein each ring of the monocyclic or polycyclic fused-ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0014] X 1 , X 2 and Z 1 are each independently C or N;

[0015] The Ir-C 1 bond is a metal-carbene bond;

[0016] Y' is selected from the group consisting of: BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR' and GeRR';

[0017] L 1Selected from the group consisting of: a direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR', C═CRR', S═O, SO2, CR, CRR', SiRR' and GeRR';

[0018] K 1 Selected from the group consisting of: a direct bond, O, S, N(R α ), P(R α ), B(R α ), C(R α )(R β ), and Si(R α )(R β );

[0019] R A and R B each independently represent mono-substituted to the maximum allowable substitution or unsubstituted;

[0020] Each R, R', R α , R β , R A and R B is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selanyl, and combinations thereof;

[0021] Any two substituents may be joined or fused to form a ring; and

[0022] L A , L B or L C Two or more of which may be joined to form a tetradentate or hexadentate ligand.

[0023] In another aspect, the present disclosure provides a formulation comprising a compound having a first ligand L A having the structure of Formula I as described herein.

[0024] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound having a first ligand L A having the structure of Formula I as described herein.

[0025] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound having a first ligand L A having the structure of Formula I as described herein. Description of the Drawings

[0026] Figure 1 Disclosed is an organic light emitting device.

[0027] Figure 2 Disclosed is an inverted organic light emitting device without an independent electron transport layer. Detailed Description

[0028] A. Terms

[0029] Unless otherwise specified, the following terms used herein are defined as follows:

[0030] As used herein, "top" means farthest from the substrate, and "bottom" means closest to the substrate. In a case where a first layer is described as being "disposed on" a second layer "above", the first layer is disposed farther from the substrate. Unless it is specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even though there are various organic layers between the cathode and the anode, the cathode can still be described as being "disposed on" the anode "above".

[0031] As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in a liquid medium in the form of a solution or a suspension and / or deposited from a liquid medium.

[0032] As used herein, and as would be generally understood by one of ordinary skill in the art, if a first energy level is closer to the vacuum level, then the 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. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On a conventional energy level diagram where the top is the vacuum level, 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 this diagram than a "lower" HOMO or LUMO energy level.

[0033] As used herein, and as would be generally understood by one of ordinary skill in the art, if the first work function has a higher absolute value, then the first work function is "greater than" or "higher than" the second work function. Since work function is typically measured as a negative number relative to the vacuum level, this means that the "higher" work function is more negative. On a conventional energy level diagram where the vacuum level is at the top, the "higher" work function is depicted as being further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow different rules than those for work function.

[0034] The present disclosure may describe layers, materials, regions, and devices in reference to the color of the light they emit. Generally, as used herein, an emission region described as producing a particular color of light may include one or more emission layers disposed on top of one another in a stacked arrangement.

[0035] As used herein, "NIR", "red", "green", "blue", "yellow" layers, materials, regions, or devices refer to layers, materials, regions, or devices that emit light within the wavelength ranges of approximately 700 - 1500 nm, 580 - 700 nm, 500 - 600 nm, 400 - 500 nm, 540 - 600 nm, respectively, or that have the highest emission spectral peak within the corresponding wavelength regions. In some arrangements, separate regions, layers, materials, or devices may provide separate "dark blue" and "light blue" emissions. As used herein, a "dark blue" emission component refers to an emission whose peak emission wavelength is at least approximately 4 nm smaller than the peak emission wavelength of a "light blue" emission component. Typically, the peak emission wavelength of the "light blue" emission component is in the range of approximately 465 - 500 nm, and the peak emission wavelength of the "dark blue" emission component is in the range of approximately 400 - 470 nm, although these ranges may vary for some configurations.

[0036] In some arrangements, a color-changing layer is provided that converts, modifies, or alters the color of the light emitted by another layer into an emission having a different wavelength. This color-changing layer may be formulated to shift the wavelength of the light emitted by another layer by a defined amount, as measured by the difference between the wavelength of the emitted light and the wavelength of the resulting light. Generally, there are two types of color-changing layers: color filters that modify the spectrum by removing light of unwanted wavelengths, and color-changing layers that convert higher-energy photons into lower-energy photons. For example, there may be a "red" filter to filter input light to remove light outside the wavelength range of approximately 580 - 700 nm. A "component" of a "color" refers to a component that, when activated or used, produces or otherwise emits light having a particular color as previously described. For example, a "first emission region of a first color" and a "second emission region of a second color different from the first color" describe two emission regions that emit two different colors as previously described when activated within a device.

[0037] As used herein, the light initially generated by a material, layer, or region is distinct from the light ultimately emitted by the same or a different structure, and the emissive materials, layers, and regions can be distinguished from each other and from other structures. Initial light generation is typically the result of a change in energy level that results in photon emission. For example, an organic emissive material can initially generate blue light, which can be converted to red or green light by a color filter, quantum dots, or other structures, such that the complete emissive stack or sub-pixel emits red or green light. In this case, the initial emissive material, region, or layer can be referred to as the "blue" component, even though the sub-pixel is a "red" or "green" component.

[0038] In some cases, it may be preferable to describe the color of a component, such as the color of an emissive region, sub-pixel, color-changing layer, etc., according to 1931 CIE coordinates. For example, a yellow emissive material can have multiple peak emission wavelengths, one in or near the edge of the "green" region and one in or near the edge of the "red" region, as previously described. Thus, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. The shape in the 1931 CIE color space is constructed by tracing the locus between two color points and any other internal points. For example, the internal shape parameters for red, green, blue, and yellow can be defined as follows:

[0039]

[0040] The terms "halo," "halogen," and "halo group" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0041] The term "acyl" refers to a substituted carbonyl (-C(O)-R s ).

[0042] The term "ester" refers to a substituted oxycarbonyl (-O-C(O)-R s or -C(O)-O-R s ) group.

[0043] The term "ether" refers to an -OR s group.

[0044] The terms "thio" or "thioether" are used interchangeably and refer to an -SR s group.

[0045] The term "selenoalkyl" refers to a -SeR s group.

[0046] The term "sulfinyl" refers to a -S(O)-R s group.

[0047] The term "sulfonyl" refers to a -SO2-Rs group

[0048] The term "phosphino" refers to a group containing at least one phosphorus atom bonded to a relevant structure. Common examples of phosphino groups include, but are not limited to, groups such as -P(R s )2 group or -PO(R s )2 group, where each R s can be the same or different.

[0049] The term "silyl" refers to a group containing at least one silicon atom bonded to a relevant structure. Common examples of silyl groups include, but are not limited to, groups such as -Si(R s )3 group, where each R s can be the same or different.

[0050] The term "germyl" refers to a group containing at least one germanium atom bonded to a relevant structure. Common examples of germyl groups include, but are not limited to, groups such as -Ge(R s )3 group, where each R s can be the same or different.

[0051] The term "boryl" refers to a group containing at least one boron atom bonded to a relevant structure. Common examples of boryl groups include, but are not limited to, groups such as -B(R s )2 group or its Lewis adduct -B(R s )3 group, where R s can be the same or different.

[0052] In each of the above, R s can be hydrogen or a substituent selected from the group consisting of general substituents as defined in the present application. Preferred R s is selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl and combinations thereof. More preferably, R s is selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof.

[0053] The term "alkyl" refers to and includes both straight-chain and branched-chain alkyls having alkyl carbon atoms bonded to a relevant structure. Preferred alkyls are alkyls containing one to fifteen carbon atoms, preferably one to nine carbon atoms, and include 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, etc. Additionally, the alkyl can be further substituted.

[0054] The term "cycloalkyl" means and includes monocyclic, polycyclic, and spirocycloalkyls having cycloalkyl carbon atoms bonded to the relevant structure. Preferred cycloalkyls are cycloalkyls having 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Additionally, the cycloalkyl can be further substituted.

[0055] The terms "heteroalkyl" or "heterocycloalkyl" mean an alkyl or cycloalkyl having at least one carbon atom replaced by a heteroatom, respectively. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocycloalkyl can be further substituted.

[0056] The term "alkenyl" means and includes both straight-chain and branched-chain alkene groups. An alkenyl is essentially an alkyl that includes at least one carbon-carbon double bond in the alkyl chain, where one carbon atom is from the carbon-carbon double bond bonded to the relevant structure. A cycloalkenyl is essentially a cycloalkyl that includes at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" means an alkenyl having at least one carbon atom replaced by a heteroatom. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Preferred alkenyls, cycloalkenyls, or heteroalkenyls are those groups having two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl can be further substituted.

[0057] The term "alkynyl" means and includes both straight-chain and branched-chain alkyne groups. An alkynyl is essentially an alkyl that includes at least one carbon-carbon triple bond in the alkyl chain, where one carbon atom is from the carbon-carbon triple bond bonded to the relevant structure. Preferred alkynyls are alkynyls having two to fifteen carbon atoms. Additionally, the alkynyl can be further substituted.

[0058] The terms "aralkyl" or "arylalkyl" are used interchangeably and mean an aryl-substituted alkyl having alkyl carbon atoms bonded to the relevant structure. Additionally, the aralkyl can be further substituted.

[0059] The term "heterocyclic group" means and includes aromatic and non-aromatic ring groups containing at least one heteroatom. Optionally, at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge, and Se, preferably O, S, N, or B. Heteroaromatic ring groups can be used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclic groups are non-aromatic heterocyclic groups containing 3 to 10 ring atoms, preferably non-aromatic heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Additionally, the heterocyclic group can be further substituted or fused.

[0060] The term "aryl" means and includes both monocyclic and polycyclic aromatic hydrocarbon groups. The polycycle can have two or more rings, where two carbons are common to two adjacent rings (the rings are "fused"). Preferred aryl groups are aryl groups containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, twelve, fourteen, or eighteen carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, fluoranthene, phenanthrene, pyrene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, and naphthalene. Additionally, the aryl group can be further substituted or fused, such as but not limited to fluorene.

[0061] The term "heteroaryl" means and includes both monocyclic aromatic groups and polycyclic aromatic ring systems having at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many cases, O, S, N, or B are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The polycyclic heterocyclic system may have two or more aromatic rings, where two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is a heteroaryl. The polycyclic heteroaromatic ring system may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryls are heteroaryls containing three to thirty carbon atoms, preferably three to twenty-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryls 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, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenophenodipyridine, azaborane, borazine, 5λ 2 ,9λ 2 -diazab-13b-boraphenanthro[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxab-13b-boraphenanthro[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diazab-13b-boraphenanthro[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxab-13b-boraphenanthro[3,2,1-de]anthracene. Additionally, the heteroaryl may be further substituted or fused.

[0062] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, 5λ 2 ,9λ 2-Diaza-13b-boraphenanthro[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boraphenanthro[3,2,1-de]anthracene groups, and their corresponding aza analogs are of particular interest.

[0063] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0064] In some cases, the preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0065] In some cases, the more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0066] In some cases, the even more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof.

[0067] In still other cases, the most preferred general substituents are selected from the group consisting of: deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0068] The terms "substituted" and "substitution" mean that a substituent other than H is bonded to the relevant position, such as carbon or nitrogen. For example, when R 1 represents a single substitution, then one R 1 must not be H (i.e., substitution). Similarly, when R 1 represents a disubstitution, then both R 1 must not be H. Similarly, when R 1 represents zero or no substitution, R 1 can, for example, be hydrogen for all available valences of the ring atoms, such as the carbon atoms of benzene and the nitrogen atom in pyrrole, or can represent only no for ring atoms with fully saturated valences, such as the nitrogen atom in pyridine. The maximum possible number of substitutions in a ring structure will depend on the total number of available valences in the ring atoms.

[0069] As used herein, "in combination" means that one or more members of an applicable list are combined to form a known or chemically stable arrangement that can be envisioned by one of ordinary skill in the art from the applicable list. By way of example, an alkyl and deuterium can be combined to form a partially or fully deuterated alkyl; a halogen and an alkyl can be combined to form a haloalkyl substituent; and a halogen, an alkyl, and an aryl can be combined to form a haloaryalkyl. In one instance, the term substituted includes combinations of two to four of the listed groups. In another instance, the term substituted includes combinations of two to three groups. In yet another instance, the term substituted includes combinations of two groups. Preferred combinations of substituents are combinations that contain up to fifty atoms that are not hydrogen or deuterium, or combinations that include up to forty atoms that are not hydrogen or deuterium, or combinations that include up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0070] As used herein, the "aza" designation in the fragments described herein, i.e., aza-dibenzofurans, aza-dibenzothiophenes, etc., means that one or more of the C-H groups in the corresponding aromatic ring can be replaced by a nitrogen atom, e.g., and without any limitation, aza-triphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed by the terms as set forth herein.

[0071] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. By way of example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US2011 / 0037057 (which are incorporated herein by reference in their entireties) describe the preparation of deuterium-substituted organometallic complexes. Further reference to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65 (which are incorporated herein by reference in their entireties) describe effective routes for the deuteration of methylene hydrogens in benzylamines and for the replacement of aromatic ring hydrogens with deuterium, respectively.

[0072] As used herein, any specifically listed substituent, such as but not limited to methyl, phenyl, pyridyl, etc. includes its non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituents such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc. also include their non-deuterated, partially deuterated, and fully deuterated forms. Unless otherwise specified, an atom in a chemical structure that does not have a valence fully occupied by H or D should be considered to include its non-deuterated, partially deuterated, and fully deuterated forms. For example, the chemical structure is meant to include C6H6, C6D6, C6H3D3, and any other of its partially deuterated variants. Some common substantially or fully deuterated groups include but are not limited to CD3, CD2C(CH3)3, C(CD3)3, and C6D5.

[0073] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written as if it were the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0074] In some cases, a pair of substituents in a molecule may optionally be joined or fused to form a ring. Preferred rings are five- to nine-membered carbocyclic or heterocyclic rings, including cases where part of the ring formed by the pair of substituents is saturated and cases where part of the ring formed by the pair of substituents is unsaturated. In still other cases, a pair of adjacent substituents may optionally be joined or fused to form a ring. As used herein, "adjacent" means that the two substituents involved may be adjacent to each other on the same ring or on two adjacent rings having the two closest available substitutable positions (such as the 2, 2'-positions in biphenyl or the 1, 8-positions in naphthalene).

[0075] B. Compounds of the Present Disclosure

[0076] In one aspect, the present disclosure provides a compound comprising a structure of formula Ir(L A ) x (L B ) y (L C ) z wherein the first ligand L A comprises a structure of formula I, and each of the ligands L B and L C is independently a bidentate ligand, where the ligands L B and L C are different. In formula Ir(L A ) x (L B ) y (LC ) z In the compound of:

[0077] x is 1, 2 or 3;

[0078] y and z are each independently 0, 1 or 2;

[0079] x + y + z = 3;

[0080] Moiety A is a polycyclic fused-ring system containing at least three rings, wherein each ring of the polycyclic fused-ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0081] Moiety A contains at least one non-benzenoid ring;

[0082] Moiety B is a monocyclic or polycyclic fused-ring system, wherein each ring of the monocyclic or polycyclic fused-ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0083] X 1 , X 2 and Z 1 each independently is C or N;

[0084] The Ir-C 1 bond is a metal-carbene bond;

[0085] Y' is selected from the group consisting of: BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR' and GeRR';

[0086] L 1 is selected from the group consisting of: a direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR' and GeRR';

[0087] K 1 is selected from the group consisting of: a direct bond, O, S, N(R α ), P(R α ), B(R α ), C(R α )(R β ) and Si(R α )(R β );

[0088] R A and R B each independently represent mono-substitution to the maximum allowable substitution or no substitution;

[0089] Each R, R', R α , R β , R A and R B is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein;

[0090] Any two substituents may be joined or fused to form a ring; and

[0091] L A , L B or L C Two or more of them may be joined to form a tetradentate or hexadentate ligand.

[0092] In some embodiments, if moiety B is a benzene ring and moiety A contains three rings, then at least one R A is selected from electron-withdrawing groups, silyl groups, and germyl groups, or moiety A contains at least one nitrogen ring atom. In some such embodiments, moiety B is a benzene ring, moiety A contains three rings, and at least one R A is selected from electron-withdrawing groups, silyl groups, and germyl groups, or moiety A contains at least one nitrogen ring atom.

[0093] In some embodiments, the first ligand L A consists essentially of Formula I. In some embodiments, the first ligand L A has the structure of Formula I.

[0094] In some embodiments, at least one of R, R', R A or R B is partially or fully deuterated. In some embodiments, at least one R A is partially or fully deuterated. In some embodiments, at least one R B is partially or fully deuterated. In some embodiments, at least one of R or R' is partially or fully deuterated. In some embodiments, at least one of R, R', R α , R β , R A and R B is a substituent selected from the group consisting of general substituents as defined herein.

[0095] In some embodiments, moiety A is a polycyclic fused-ring system containing at least three rings, wherein each ring of the polycyclic fused-ring system is independently a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, moiety A is a polycyclic fused-ring system containing at least three rings, wherein each ring of the polycyclic fused-ring system is independently a 5- or 6-membered aryl ring or heteroaryl ring.

[0096] In some embodiments, moiety B is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, moiety B is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- or 6-membered aryl or heteroaryl ring.

[0097] In some embodiments, each R, R', R α , R β , R A and R B is independently hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein. In some embodiments, each R, R', R α , R β , R A and R B is independently hydrogen or a substituent selected from the group consisting of the more preferred general substituents defined herein. In some embodiments, each R, R', R α , R β , R A and R B is independently hydrogen or a substituent selected from the group consisting of the most preferred general substituents defined herein.

[0098] In some embodiments, x is 1. In some embodiments, y is 2. In some embodiments, y is 1 and z is 1.

[0099] In some embodiments, x is 2 and y is 1.

[0100] In some embodiments, x is 3.

[0101] In some embodiments, moiety B is selected from the group consisting of the following list of cyclic groups: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzobenzimidazole, aza-benzobenzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene and aza-fluorene. In some embodiments, the aza-variants include one N located on the benzo-ring. In some embodiments, the aza-variants include one N located on the benzo-ring and the N is bonded to the metal M.

[0102] In some embodiments, moiety B is a monocyclic ring. In some embodiments, moiety B is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, moiety B is benzene.

[0103] In some embodiments, moiety B is a fused polycyclic system. In some embodiments, moiety B is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzo-benzimidazole, aza-benzo-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, moiety B is selected from the group consisting of naphthalene.

[0104] In some embodiments, moiety A has 3 rings and is selected from the group consisting of: carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0105] In some embodiments, moiety B can be a polycyclic fused ring structure. In some embodiments, moiety B can be a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to the Ir atom and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, moiety B can be selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene, and their aza-variants. In some such embodiments, moiety B can be further substituted at the ortho or meta position of the O, S, or Se atom with a substituent selected from the group consisting of: deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza-variant contains exactly one N atom at the 6-position (ortho to O, S, or Se) and a substituent at the 7-position (meta to O, S, or Se).

[0106] In some embodiments, moiety B can be a polycyclic fused-ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused-ring structure comprises three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to the Ir atom, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0107] In some embodiments, moiety B can be a polycyclic fused-ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused-ring structure comprises four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments having one 5-membered ring, the 5-membered ring is fused to the ring coordinated to the Ir atom, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third 6-membered ring.

[0108] In some embodiments, moiety B can be the aza form of the polycyclic fused-ring described above. In some such embodiments, moiety B can contain exactly one aza N atom. In some such embodiments, moiety B contains exactly two aza N atoms, which can be in one ring or in two different rings. In some such embodiments, the ring having the aza N atom is separated from the Ir atom by at least two other rings. In some such embodiments, the ring having the aza N atom is separated from the Ir atom by at least three other rings. In some such embodiments, each of the ortho positions of the aza N atom is substituted.

[0109] In some embodiments, moiety A comprises at least 4 rings. In some embodiments, moiety A comprises at least 5 rings. In some embodiments, moiety A comprises at least 6 rings. In some embodiments, moiety A comprises indolocarbazole.

[0110] In some embodiments, moiety A comprises at least one nitrogen ring atom. In some embodiments, moiety A is formed by one 5-membered ring and at least three benzene rings. In some such embodiments, the 5-membered ring is furan.

[0111] In some embodiments, moiety A is formed by two 5-membered rings and at least three benzene rings. In some such embodiments, the two 5-membered rings are separated by at least one benzene ring. In some embodiments, the two 5-membered rings are fused together.

[0112] In some embodiments, moiety A comprises a group containing Y'-C 1 -X 1a first portion A1 that is ring-fused, and portion A1 is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzo-benzimidazole, aza-benzo-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, aza-phenanthrene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, the first portion A1 is dibenzofuran, aza-dibenzofuran, or carbazole.

[0113] In some embodiments, portion A further comprises a second portion A2 that is cyclized to the first portion A1, wherein the second portion A2 is selected from the group consisting of the list of cyclic groups defined herein. In some embodiments, the second portion A2 is benzene, naphthalene, or indole.

[0114] In some embodiments, portion A1 is dibenzofuran and portion A2 is benzene or naphthalene. In some such embodiments, portion A2 is benzene. In some such embodiments, portion A2 is naphthalene.

[0115] In some embodiments, X 1 is N. In some embodiments, X 2 is C.

[0116] In some embodiments, Z 1 is C. In some embodiments, Z 1 is N.

[0117] In some embodiments, K 1 is a direct bond.

[0118] In some embodiments, K 1 is O or S. In some embodiments, K 1 is O. In some embodiments, K 1 is N(R α ), P(R α ), or B(R α ). In some embodiments, K 1 is C(R α )(R β ), or Si(R α )(R β ).

[0119] In some embodiments, Y' is selected from the group consisting of O, S, and Se.

[0120] In some embodiments, Y' is selected from the group consisting of BR, NR, and PR. In some such embodiments, R is an alkyl or a partially or fully deuterated alkyl. In some such embodiments, R is a methyl or a partially or fully deuterated methyl.

[0121] In some embodiments, Y' is NR. In some such embodiments, R is an alkyl or a partially or fully deuterated alkyl. In some such embodiments, R is a methyl or a partially or fully deuterated methyl.

[0122] In some embodiments, R in Y' has the structure wherein R EE each independently represents zero substitution, mono-substitution, or up to the maximum allowable substitution; and R EE , R EE0 , R EE1 and R EE2 each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein.

[0123] In some embodiments, R EE0 is selected from the group consisting of: halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selanyl, and combinations thereof. In some embodiments, R EE1 is the same as R EE2 . In some embodiments, R EE1 is different from R EE2 . In some embodiments, at least one of R EE1 and R EE2 contains a chemical group having at least three 6-membered aromatic rings that are not fused to each other. In some embodiments, at least one of R EE1 and R EE2 contains a chemical group having at least four 6-membered aromatic rings that are not fused to each other. In some embodiments, at least one of R EE1 and R EE2 contains a chemical group having at least five 6-membered aromatic rings that are not fused to each other. In some embodiments, at least one of R EE1 and R EE2 contains a chemical group having at least six 6-membered aromatic rings that are not fused to each other. In some embodiments, at least one of R EE1 and R EE2Both contain chemical groups having at least three to six 6-membered aromatic rings, and the adjacent aromatic rings are not fused to each other. In some embodiments, R EE1 and R EE2 at least one of which contains a group R having a structure selected from the group consisting of W : Formula IIIA, ---Q A (R 1a )(R 2a ) a (R 3a ) b , Formula IIIB, and Formula IIIC, wherein

[0124] Each of R SS , R TT and R UU independently represents mono-substituted to the maximum allowable number of substitutions or unsubstituted;

[0125] Each of X 130 to X 138 is independently C or N;

[0126] Each of Y S , Y T and Y U is independently CRR', SiRR' or GeRR';

[0127] n is an integer between 1 and 8, and when n exceeds 1, each Y S can be the same or different;

[0128] Q A is selected from the group consisting of: C, Si, Ge, N, P, O, S, Se and B;

[0129] a and b are each independently 0 or 1;

[0130] When Q A is C, Si or Ge, a + b = 2;

[0131] When Q A is N or P, a + b = 1;

[0132] When Q A is B, a + b can be 1 or 2;

[0133] When Q A is O, S or Se, a + b = 0;

[0134] Each R, R', R 1a , R 2a , R 3a , RSS , R TT and R UU are independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;

[0135] And any two substituents may optionally be fused or joined to form a ring.

[0136] In some embodiments, at least one of R EE1 and R EE2 contains the group R W . In some embodiments, both R EE1 and R EE2 independently contain the group R W . In some embodiments, both R EE1 and R EE2 independently contain Formula IIIA. In some embodiments, both R EE1 and R EE2 independently contain Formula IIIB. In some embodiments, both R EE1 and R EE2 independently contain Formula IIIC. In some embodiments, one of R EE1 and R EE2 contains Formula IIIA, and the other of R EE1 and R EE2 contains Formula IIIB. In some embodiments, one of R EE1 and R EE2 contains Formula IIIA, and the other of R EE1 and R EE2 contains Formula IIIC. In some embodiments, one of R EE1 and R EE2 contains Formula IIIB, and the other of R EE1 and R EE2 contains Formula IIIC.

[0137] In some embodiments, the molecular weight (MW) of R EE1 is greater than 15 g / mol and the molecular weight of R EE2 is greater than that of R EE1 . In some embodiments, the molecular weight (MW) of R EE1 is greater than 56 g / mol and the molecular weight of R EE2 is greater than that of R EE1 . In some embodiments, the molecular weight (MW) of R EE1 is greater than 76 g / mol and the molecular weight of R EE2 is greater than that of R EE1 . In some embodiments, the molecular weight (MW) of R EE1 is greater than 81 g / mol and the molecular weight of R EE2has a molecular weight greater than R EE1 . In some embodiments, R EE1 or R EE2 has a molecular weight (MW) greater than 165 g / mol. In some embodiments, R EE1 or R EE2 has a molecular weight (MW) greater than 166 g / mol. In some embodiments, R EE1 or R EE2 has a molecular weight (MW) greater than 182 g / mol. In some embodiments, R EE1 has one more 6-membered aromatic ring than R EE2 . In some embodiments, R EE1 has two more 6-membered aromatic rings than R EE2 . In some embodiments, R EE1 has three more 6-membered aromatic rings than R EE2 . In some embodiments, R EE1 has four more 6-membered aromatic rings than R EE2 . In some embodiments, R EE1 has five more 6-membered aromatic rings than R EE2 . In some embodiments, R EE1 contains at least one heteroatom and R EE2 consists of hydrocarbons and their deuterated variants. In some embodiments, R EE1 contains at least two heteroatoms and R EE2 consists of hydrocarbons and their deuterated variants. In some embodiments, R EE1 contains at least three heteroatoms and R EE2 consists of hydrocarbons and their deuterated variants. In some embodiments, R EE1 contains exactly one heteroatom and R EE2 consists of hydrocarbons and their deuterated variants. In some embodiments, R EE1 contains exactly two heteroatoms and R EE2 consists of hydrocarbons and their deuterated variants. In some embodiments, R EE1 contains exactly three heteroatoms and R EE2 consists of hydrocarbons and their deuterated variants. In some embodiments, R EE1 contains exactly one heteroatom, and R EE2 contains exactly one heteroatom different from the heteroatom in R EE1 . In some embodiments, R EE1 contains exactly one heteroatom, and R EE2 contains exactly one heteroatom identical to the heteroatom in R EE1 .

[0138] In some embodiments, R EE1Contains exactly two heteroatoms and R EE2 Contains exactly one heteroatom. In some embodiments, R EE1 Contains exactly two heteroatoms and R EE2 Contains exactly two heteroatoms. In some embodiments, R EE1 Contains exactly three heteroatoms and R EE2 Contains exactly one heteroatom. In some embodiments, R EE1 Contains exactly three heteroatoms and R EE2 Contains exactly two heteroatoms. In some embodiments, R EE1 Contains exactly three heteroatoms and R EE2 Contains exactly three heteroatoms.

[0139] In some embodiments, R EE1 and R EE2 At least one of which contains an aromatic ring fused to a non-aromatic ring. In some embodiments, R EE1 and R EE2 Both contain an aromatic ring fused to a non-aromatic ring. In some embodiments, the aromatic ring is a phenyl ring and the non-aromatic ring is a cycloalkyl ring. In some embodiments, R EE1 and R EE2 At least one of which is partially or fully deuterated. In some embodiments, R EE1 and R EE2 Are both partially or fully deuterated.

[0140] In some embodiments, Y' is selected from the group consisting of: BRR', CRR', SiRR' and GeRR'. In some embodiments, Y' is selected from the group consisting of: P(O)R, C═O, C═S, C═Se, C═NR, C═CRR', S═O and SO2. In some embodiments, Y' is selected from CR.

[0141] In some embodiments, L 1 Is a direct bond.

[0142] In some embodiments, L 1 Is selected from the group consisting of O, S and Se.

[0143] In some embodiments, L 1 Is selected from the group consisting of BR, NR and PR. In some such embodiments, R is bonded or fused to R A or R B In some such embodiments, R is an aryl and is bonded or fused to R A or R B In some such embodiments, R is bonded or fused to R A In some such embodiments, R is bonded or fused to RB Bonding or fusion. In some such embodiments, L 1 is NR.

[0144] In some embodiments, L 1 is selected from the group consisting of BRR', CRR', SiRR', and GeRR'. In some embodiments, L 1 is selected from the group consisting of P(O)R, C═O, C═S, C═Se, C═NR, C═CRR', S═O, and SO2. In some embodiments, L 1 is selected from CR.

[0145] In some embodiments, the compound comprises an electron-withdrawing group. In some embodiments of the compound, the electron-withdrawing group has a Hammett constant greater than 0. In some embodiments, the Hammett constant of the electron-withdrawing group is equal to or greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

[0146] In some embodiments, the first ligand L A comprises an electron-withdrawing group selected from the following list of EWG1: F, CF3, CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3, (R k2 )2CCN, (R k2 )2CCF3, CNC(CF3)2, BR k3 R k2 , substituted or unsubstituted dibenzoborolene, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, alkyl containing a cyano group, aryl containing a cyano group, heteroaryl containing a cyano group, isocyanate,

[0147] Where each R k1 represents mono-substitution to the maximum allowable substitution or no substitution;

[0148] Where Y G is selected from the group consisting of: BR e , NR e , PR e , O, S, Se, C═O, S═O, SO2, CR e R f , SiR e R f , and GeR e R f' ; and

[0149] Where R k1 , R k2 , R k3 , R e , and R f each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halogen group, alkyl group, cycloalkyl group, heteroalkyl group, aralkyl group, alkoxy group, aryloxy group, amino group, silyl group, germanium alkyl group, boron alkyl group, alkenyl group, cycloalkenyl group, heteroalkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, carbonyl group, carboxylic acid, ester, nitrile, isonitrile, sulfhydryl group, selenium alkyl group, sulfinyl group, sulfonyl group, phosphino group and combinations thereof.

[0150] In some embodiments, the first ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG2 list:

[0151]

[0152]

[0153] In some embodiments, the first ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG3 list:

[0154]

[0155] In some embodiments, the first ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG4 list:

[0156] In some embodiments, the first ligand L A comprises an electron-withdrawing group, which is a π-deficient electron-withdrawing group. In some embodiments, the π-deficient electron-withdrawing group is selected from the group consisting of the structures in the following Pi-EWG list: CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3, BR k2 R k3 , substituted or unsubstituted dibenzoborolene, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, aryl containing a cyano group, heteroaryl containing a cyano group, isocyanate, wherein the variables are the same as those defined previously.

[0157] In some embodiments, the compound comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0158] In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R Ais or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0159] In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0160] In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0161] In some embodiments, L B comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0162] In some embodiments, L C comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L C comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L C comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L C comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L C comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0163] In some embodiments, at least one R A is not H. In some embodiments, each R A is H. In some embodiments, at least one R A comprises at least one C atom. In some embodiments, at least one R A comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, electron-withdrawing group, and combinations thereof.

[0164] In some embodiments, at least one R on the last or penultimate ring of moiety A A comprises an electron-withdrawing group. In some embodiments, at least one R on the last ring of moiety A A comprises an electron-withdrawing group. In some embodiments, at least one R on the penultimate ring of moiety A A comprises an electron-withdrawing group. As used herein, the "last" ring refers to the ring furthest from the Ir atom, and the "penultimate" ring refers to the ring second furthest from the Ir atom.

[0165] In some embodiments, at least one R A is selected from the group consisting of an electron-withdrawing group, silyl, and germyl.

[0166] In some embodiments, at least one R on the last ring of moiety A A is an electron-withdrawing group, silyl, or germyl. In some embodiments, at least one R on the last ring of moiety A A is an electron-withdrawing group. In some embodiments, at least one R on the last ring of moiety A A is a -CN moiety. In some embodiments, at least one R on the last ring of moiety A A is a silyl moiety. In some embodiments, at least one R on the last ring of moiety A A is a germyl moiety.

[0167] In some embodiments, at least one R on the penultimate ring of moiety A A is an electron-withdrawing group, a silyl group, or a germyl group. In some embodiments, at least one R on the penultimate ring of moiety A A is an electron-withdrawing group. In some embodiments, at least one R on the penultimate ring of moiety A A is a -CN moiety. In some embodiments, at least one R on the penultimate ring of moiety A A is a silyl moiety. In some embodiments, at least one R on the penultimate ring of moiety A A is a germyl moiety.

[0168] In some embodiments, at least one R B is not H. In some embodiments, each R B is H. In some embodiments, at least one R B contains at least one C atom. In some embodiments, at least one R B contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0169] In some embodiments, moiety B is a benzene ring and moiety A has three rings. In some such embodiments, at least one R A is selected from the group consisting of an electron-withdrawing group, a silyl group, and a germyl group. In some such embodiments, moiety A contains at least one nitrogen ring atom. In some embodiments, moiety A contains a pyridine ring or a pyrrole ring. In some embodiments, moiety A contains a pyridine ring. In some embodiments, moiety A contains a pyrrole ring.

[0170] In some embodiments, the first ligand L A is selected from the group consisting of the structures of List 1 below:

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190] Wherein:

[0191] X 3 to X 37 each and every occurrence of X is independently C or N;

[0192] Each Y A1 、Y A2 、Y A3 and Y B is independently selected from the group consisting of: BR e 、NR e 、PR e 、O, S, Se, C=O, S=O, SO2, CR e R f 、SiR e R f and GeR e R f ;

[0193] R A ' and R B ' each independently represents mono-substituted to the maximum possible number of substitutions or unsubstituted;

[0194] Each R e 、R f 、R A '、R B ' and R N is independently hydrogen or a substituent selected from the group of general substituents as defined herein;

[0195] And any two substituents may be joined or fused to form a ring.

[0196] In some embodiments, at least one of R e , R f , R A ', R B ', R N is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments where the ligand L A is selected from List 1, at least one of R e , R f , R A ', R B ', R N is partially or fully deuterated. In some embodiments, at least one R A ' is partially or fully deuterated. In some embodiments, at least one R B ' is partially or fully deuterated. In some embodiments, R N is partially or fully deuterated. In some embodiments, at least one of R e or R f is partially or fully deuterated. In some embodiments, R N does not coordinate to the metal. In some embodiments, each of X 3 to X 37 is C.

[0197] In some embodiments where the ligand L A is selected from List 1, at least one R A ' is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A ' is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A ' is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A ' is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A ' is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0198] In some embodiments where the ligand L A is selected from List 1, at least one R B ' is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B'is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B 'is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B 'is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B 'is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0199] In ligand L A In some embodiments where it is selected from List 1, at least one R N is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R N is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R N is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R N is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R N is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0200] In ligand L A In some embodiments where it is selected from List 1, at least one R e or R f is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R e or R f is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R e or R f is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R e or R f is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R e or R f is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0201] In some embodiments, ligand L A is selected from the group consisting of the structures of the following List 2:

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218] Wherein:

[0219] Y A1 , Y A2 , Y A3 , Y A4 and Y B each independently is selected from the group consisting of: BR e , NR e , PR e , O, S, Se, C═O, S═O, SO2, CR e R f , SiR e R f and GeR e R f ;

[0220] R A ' and R B ' each independently represents mono-substituted to the maximum possible number of substitutions or unsubstituted;

[0221] Each R e 、R f 、R A '、R B ' and R N is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein;

[0222] And any two substituents may be joined or fused to form a ring.

[0223] In some embodiments where the ligand L A is selected from List 2, at least one of R e 、R f 、R A '、R B '、R N is partially or fully deuterated. In some embodiments, at least one R A ' is partially or fully deuterated. In some embodiments, at least one R B ' is partially or fully deuterated. In some embodiments, R N is partially or fully deuterated. In some embodiments, at least one of R e or R f is partially or fully deuterated.

[0224] In some embodiments where the ligand L A is selected from List 2, at least one R A ' is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A ' is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A ' is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A ' is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A ' is or contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0225] In some embodiments where the ligand L A is selected from List 2, at least one R B ' is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B ' is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B ' is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one RB 'is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B 'is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0226] In ligand L A In some embodiments selected from List 2, at least one R N is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R N is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R N is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R N is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R N is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0227] In ligand L A In some embodiments selected from List 2, at least one R e or R f is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R e or R f is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R e or R f is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R e or R f is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R e or R f is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0228] In some embodiments, ligand L A is selected from the group consisting of L Ai where i is an integer from 1 to 179; where L A1 to L A179 are each defined in List 3 below:

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239] In some embodiments, the compound has a formula selected from the group consisting of: Ir(L A )3, Ir(L A )(L B )2, Ir(L A )2(L B ), Ir(L A )2(L C ), and Ir(L A )(L B )(L C ); and wherein L A , L B , and L C are different from each other. In some embodiments, L B is a substituted or unsubstituted phenylpyridine, and L C is a substituted or unsubstituted acetylacetonate.

[0240] In some embodiments, L B and L C are each independently selected from the group consisting of the structures of List 4 below:

[0241]

[0242]

[0243]

[0244] Wherein:

[0245] T is selected from the group consisting of: B, Al, Ga, and In;

[0246] K 1'is selected from the group consisting of: a single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ;

[0247] Y 1 to Y 13 each independently is selected from the group consisting of C and N;

[0248] Y'is selected from the group consisting of: BR e , BR e R f , NR e , PR e , P(O)R e , O, S, Se, C═O, C═S, C═Se, C═NR e , C═CR e R f , S═O, SO2, CR e R f , SiR e R f and GeR e R f ;

[0249] R e and R f can be fused or joined to form a ring;

[0250] each R a , R b , R c and R d independently represents mono-substituted to the maximum allowable number of substitutions or unsubstituted;

[0251] R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f each independently is hydrogen or a substituent selected from the group of general substituents defined herein; and

[0252] R a1 , R b1 , R c1 , R d1 , R a , Rb , R c and R d Any two substituents in may be fused or joined to form a ring or form a polydentate ligand.

[0253] In some embodiments, L B and L C are each independently selected from the group consisting of the structures of List 5 below:

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261] Wherein:

[0262] R a ', R b ', R c ', R d ', and R e ' each independently represent zero substitution, mono-substitution or up to the maximum allowable number of substitutions on their associated ring;

[0263] R a ', R b ', R c ', R d ', and R e ' are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and

[0264] R a ', R b ', R c ', R d ', and R e ' may be fused or joined to form a ring or form a polydentate ligand.

[0265] In some embodiments, L B comprises the following structure: wherein all variables are the same as those defined previously. In some embodiments, Y 1 to Y 4Each of them is carbon independently. In some embodiments, Y 1 to Y 4 At least one of them is N. In some embodiments, Y 1 to Y 4 Exactly one of them is N. In some embodiments, Y 1 is N. In some embodiments, Y 2 is N. In some embodiments, Y 3 is N. In some embodiments, Y 4 is N. In some embodiments, at least one R a is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, at least one R a is a tertiary alkyl group. In some embodiments, Y 3 is C, and the R a connected thereto is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, Y 1 to Y 3 are C, Y 4 is N, and the R 3 connected to Y a is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, Y 1 to Y 3 are C, Y 4 is N, and the R 2 connected to Y a is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, at least one R b is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, the tertiary alkyl group is tert-butyl. In some embodiments, at least one pair of R a , a pair of R b or a pair of R a and R b join or condense to form a ring.

[0266] In some embodiments, the first ligand L A can be selected from L Ai , where i is an integer from 1 to 179; and L B can be selected from L Bk , where k is an integer from 1 to 530, where:

[0267] When the compound has the formula Ir(L Ai )3, the compound is selected from the group consisting of: Ir(L A1 )3 to Ir(L A179 )3;

[0268] When the compound has the formula Ir(L Ai )(L Bk) When it is 2, the compound is selected from the group consisting of: Ir(L A1 )(L B1 )2 to Ir(L A179 )(L B530 )2;

[0269] When the compound has the formula Ir(L Ai )2(L Bk ), the compound is selected from the group consisting of: Ir(L A1 )2(L B1 ) to Ir(L A179 )2(L B530 );

[0270] When the compound has the formula Ir(L Ai )2(L Cj-I ), j is an integer from 1 to 1416, where the compound is selected from the group consisting of: Ir(L A1 )2(L C1-I ) to Ir(L A179 )2(L C1416-I ); and

[0271] When the compound has the formula Ir(L Ai )2(L Cj-II ), j is an integer from 1 to 1416, where the compound is selected from the group consisting of: Ir(L A1 )2(L C1-II ) to Ir(L A179 )2(L C1416-II );

[0272] Where each L Bk has the structure defined in List 6 below:

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286] where each L Cj-I has a structure based on the following formula: and

[0287] each L Cj-II has a structure based on the following formula: where for each L Cj-I and L Cj-II in L Cj , R 201 and R 202 are defined in List 7 below:

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297] where R D1 to R D246 have the structures defined in List 8 below:

[0298]

[0299]

[0300]

[0301]

[0302] In some embodiments, the compound is selected only from those compounds consisting of its L Bk corresponding to one of the following: L B1 、L B2 、L B18 、L B28 、L B38 、L B108 、L B118 、L B122 、L B124 、L B126 、L B128 、L B130 、L B132 、L B134 、L B136 、L B138 、L B140 、L B142 、L B144 、L B156 、L B158 、L B160 、L B162 、L B164 、L B168 、L B172 、L B175 、L B204 、L B206 、L B214 、L B216 、L B218 、L B220 、L B222 、L B231 、L B233 、L B235 、L B237 、L B240 、L B242 、L B244 、L B246 、L B248 、L B250 、L B252 、L B254 、L B256 、L B258 、L B260 、L B262 、L B264 、L B265 、L B266 、L B267 、L B268 、L B269 and L B270 。

[0303] In some embodiments, the compound is selected only from those compounds consisting of its L BkThe group consisting of those compounds corresponding to one of the following: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B126 , L B128 , L B132 , L B136 , L B138 , L B142 , L B156 , L B162 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B231 , L B233 , L B237 , L B264 , L B265 , L B266 , L B267 , L B268 , L B269 and L B270 .

[0304] In some embodiments, compounds are selected only from the group consisting of Cj-I or L Cj-II The group of compounds consisting of ligands, the corresponding R 201 and R 202 is defined as one of the following structures: R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D18 , R D20 , R D22 , R D37 , R D40 , R D41 , R D42 , R D43 , R D48 , R D49 , R D50 , R D54 , R D55 , R D58 , R D59 , R D78 , R D79 , RD81 , R D87 , R D88 , R D89 , R D93 , R D116 , R D117 , R D118 , R D119 , R D120 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D147 , R D149 , R D151 , R D154 , R D155 , R D161 , R D175 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 and R D246 .

[0305] In some embodiments, the compound is selected only from the group consisting of those compounds having an L Cj-I or L Cj-II ligand, and the corresponding R 201 and R 202 of the ligand are defined as being selected from one of the following structures: R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D22 , R D43 , R D50 , R D78 , R D116 , R D118 , R D133 , R D134, R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D149 , R D151 , R D154 , R D155 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 and R D246 .

[0306] In some embodiments, the compound is selected only from the group consisting of those compounds having one of the structures of Listing 9 for the L Cj-I ligand:

[0307]

[0308]

[0309]

[0310] In some embodiments, the compound has a formula selected from the group consisting of: Ir(L A )3, Ir(L A )2(L B ), Ir(L A )(L B )2, Ir(L A )2(L C ), and Ir(L A )(L B )(L C ). In some embodiments, L A is selected from the group consisting of the structures in Listing 1, Listing 2, and Listing 3, L B is selected from the group consisting of the structures in Listing 4, Listing 5, and Listing 6 (L Bk ), and L C is selected from the L as defined hereinCj-I and L Cj-II a group consisting of the structures of.

[0311] In some embodiments, L A is selected from the group consisting of the structures of List 1, and L B is selected from the group consisting of L Bk 's structure. In some embodiments, L A is selected from the group consisting of the structures of List 2, and L B is selected from the group consisting of L Bk 's structure. In some embodiments, L A is selected from List 3 as defined herein, and L B is selected from the group consisting of L Bk 's structure, where k is an integer from 1 to 530. In some embodiments, L A is selected from List 3 as defined herein, and L C is selected from the group consisting of L Cj-I and L Cj-II 's structure, where j is an integer from 1 to 1416.

[0312] In some embodiments, the compound may have the formula Ir(L Ai )3, which consists of the following compounds: Ir(L A1 )3 to Ir(L A179 )3. The compound may have the formula Ir(L Ai )(L B )2, which consists of the following compounds: Ir(L A1 )(L B )2 to Ir(L A179 )(L B )2. The compound may have the formula Ir(L Ai )2(L B ), which consists of the following compounds: Ir(L A1 )2(L B ) to Ir(L A179 )2(L B ). The compound may have the formula Ir(L A )(L Bk )2, which consists of the following compounds: Ir(L A )(L B1 )2 to Ir(L A )(L B530 )2. The compound may have the formula Ir(L A )2(L Bk ), which consists of the following compounds: Ir(L A )2(L B1 ) to Ir(LA ) 2(L B530 )。The compound may have the formula Ir(L Ai )(L Bk )2, which consists of the following compounds: Ir(L A1 )(L B1 )2 to Ir(L A179 )(L B530 )2. The compound may have the formula Ir(L Ai )2(L Bk ),which consists of the following compounds: Ir(L A1 )2(L B1 ) to Ir(L A179 )2(L B530 )。The compound may have the formula Ir(L Ai )2(L Cj-I ),which consists of the following compounds: Ir(L A1 )2(L C1-I ) to Ir(L A179 )2(L C1416-I )。The compound may have the formula Ir(L Ai )2(L Cj-II ),which consists of the following compounds: Ir(L A1 )2(L C1-II ) to Ir(L A179 )2(L C1416-II )。The compound may have the formula Ir(L Ai )(L Bk )(L Cj-I ),which consists of the following compounds: Ir(L A1 ))(L B1 )(L C1-I ) to Ir(L A179 )(L B530 )(L C1416-I )。The compound may have the formula Ir(L Ai )(L Bk )(L Cj-II ),which consists of the following compounds: Ir(L A1 )(L B1 )(L C1-II ) to Ir(L A179 )(L B530 )(L C1416-II )。

[0313] In some embodiments, the compound is selected from the group consisting of the structures in the following List 10:

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320] In some embodiments, the first ligand L of formula I described herein A compounds can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percentage of deuteration has its ordinary meaning and includes the percentage of all possible hydrogen atoms (e.g., positions of hydrogen or deuterium) occupied by deuterium atoms in the compound. In some embodiments, the carbon atoms constituting the ring coordinated to metal M are fully or partially deuterated. In some embodiments, the carbon atoms contained in the polycyclic system coordinated to metal M are fully or partially deuterated. In some embodiments, the substituents attached to the monocyclic or fused polycyclic system coordinated to metal M are fully or partially deuterated.

[0321] In some embodiments, the emission of the compound of formula I at room temperature has a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM means better color purity for OLED display applications.

[0322] In some embodiments of the heteroleptic compound having the formula Ir(L A ) x (L B ) y (L C ) z the ligand L A has a first substituent R I , where the first atom a-I in the first substituent R I is the farthest from metal M among all the atoms of the ligand L A . Additionally, the ligand L B (if present) has a second substituent R II , where the first atom a-II in the second substituent R II is the farthest from metal M among all the atoms of the ligand L B . Further, the ligand L C (if present) has a third substituent R III, where the third substituent R III The first atom a-III in C is the farthest from the metal M among all the atoms of the ligand L.

[0323] In such heteroleptic compounds, a vector V can be defined as follows D1 , V D2 and V D3 . V D1 represents the direction from the metal M to the first atom a-I, and the value D D1 of the vector V 1 represents the straight-line distance between the metal M and the first atom a-I in the first substituent R I . V D2 represents the direction from the metal M to the first atom a-II, and the value D D2 of the vector V 2 represents the straight-line distance between the metal M and the first atom a-II in the second substituent R II . V D3 represents the direction from the metal M to the first atom a-III, and the value D D3 of the vector V 3 represents the straight-line distance between the metal M and the first atom a-III in the third substituent R III .

[0324] In such heteroleptic compounds, a sphere with a radius r is defined, whose center is the metal M and the radius r is the minimum radius allowing the sphere to enclose all the atoms of the compound that are not part of the substituents R I , R II and R III ; and where at least one of D 1 , D 2 and D 3 is at least larger than the radius r. In some embodiments, at least one of D 1 , D 2 and D 3 is at least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or In some embodiments, at least two of D 1 , D 2 and D 3 are at least 1.5, 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or

[0325] In some embodiments of such heteromeric compounds, the compound has a transition dipole moment axis, and the angle between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 is defined, wherein the angle between the transition dipole moment axis and at least one of the vectors V D1 、V D2 and V D3 is less than 40°. In some embodiments, the angle between the transition dipole moment axis and at least one of the vectors V D1 、V D2 and V D3 is less than 30°, 20°, 15° or 10°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 are less than 20°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 are less than 15° or 10°.

[0326] In some embodiments, all three of the angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 are less than 20°. In some embodiments, all three of the angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 are less than 15° or 10°.

[0327] In some embodiments of such heteromeric compounds, the compound has a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteromeric compounds, the compound has a VDR of 0.30, 0.25, 0.20 or 0.15 or less.

[0328] One of ordinary skill in the art will readily understand the meaning of the terms transition dipole moment axis of a compound and vertical dipole ratio of a compound. However, the meaning of these terms can be found in U.S. Patent No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. Patent No. 10,672,997, the horizontal dipole ratio (HDR) of a compound is discussed rather than the VDR. However, one of ordinary skill in the art will readily understand that VDR = 1 - HDR.

[0329] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence, triplet-triplet annihilation, or a combination of these methods. In some embodiments, the emissive dopant can be a racemic mixture or can be enriched in one enantiomer. In some embodiments, the compounds of the present invention can have different stereoisomers, such as fac and mer. The present compounds relate to individual isomers and mixtures of various isomers in any mixing ratio. In some embodiments, the compound can be homoleptic (each ligand being the same). In some embodiments, the compound can be heteroleptic (at least one ligand being different from the others). In some embodiments, when there is more than one ligand coordinating to the metal, the ligands can all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, each ligand can be different from all the other ligands. This also holds in embodiments where the ligands coordinating to the metal can be linked to other ligands coordinating to the metal to form tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, in cases where the coordinating ligands are linked together, in some embodiments, all the ligands can be the same, and in some other embodiments, at least one of the linked ligands can be different from the other ligands.

[0330] In yet another aspect of the present disclosure, a formulation comprising a novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of solvents, emitters, hosts, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials disclosed herein.

[0331] The present disclosure encompasses any chemical structure that includes the novel compounds of the present disclosure or their monovalent or polyvalent variants. In other words, the inventive compounds or their monovalent or polyvalent variants can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of: monomers, polymers, macromolecules, and supramolecules (also known as supermolecules). As used herein, a "monovalent variant of a compound" refers to the same moiety as the compound, but with one hydrogen removed and replaced with a bond connecting to the remainder of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to the same moiety as the compound, but with more than one hydrogen removed and replaced with one or more bonds connecting to the remainder of the chemical structure. In the case of a supramolecule, the inventive compounds can also be incorporated into the supramolecular complex without covalent bonds. As used in this context, the description that structure A contains moiety B means that structure A includes the structure of moiety B, and the structure of moiety B does not include H or D atoms that can be attached to moiety B. This is because at least one H or D on a given moiety structure must be replaced with a substituent such that moiety B can be part of structure A, and after it becomes part of structure A, one or more of the H or D on the given moiety B structure can be further substituted.

[0332] C. OLEDs and Devices of the Present Disclosure

[0333] In another aspect, the present disclosure also provides an OLED device that includes a first organic layer containing a compound as disclosed in the above compound section of the present disclosure.

[0334] In some embodiments, the OLED includes: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer contains a compound having a structure of formula Ir(L A ) x (L B ) y (L C ) z as defined herein.

[0335] In some embodiments, the organic layer is selected from the group consisting of: HIL, HTL, EBL, EML, HBL, ETL, and EIL. In some embodiments, the organic layer can be an emissive layer and the compound as described herein can be an emissive dopant or a non-emissive dopant.

[0336] In some embodiments, the organic layer can further include a host, wherein the host contains at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2-Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, azacyclohexaborane, oxaborole, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzooxasiline, phenoxazine, phenoxathiin, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boranyl, silyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

[0337] In some embodiments, the host may be selected from the group consisting of the structures in Host Group 1 below:

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348] Wherein:

[0349] Each of J1 to J6 is independently C or N;

[0350] L' is a direct bond or an organic linking group;

[0351] Each Y AA 、Y BB 、Y CC and Y DDIndependently selected from the group consisting of: no bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0352] R A ', R B ', R C ', R D ', R E ', R F ' and R G ' each independently represents mono-substituted, up to maximum substitution or unsubstituted;

[0353] Each R, R', R A ', R B ', R C ', R D ', R E ', R F ' and R G ' are independently hydrogen or a substituent selected from the group of general substituents as defined herein; any two substituents may be joined or fused to form a ring;

[0354] And, where possible, each unsubstituted aromatic carbon atom is optionally replaced by one or more N to form a nitrogen-substituted ring.

[0355] In some embodiments, at least one of J1 to J3 is N. In some embodiments, at least two of J1 to J3 are N. In some embodiments, all three of J1 to J3 are N. In some embodiments, each Y CC and Y DD are independently O, S or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced by N to form a nitrogen heterocycle.

[0356] In some embodiments, the host is selected from the group consisting of: EG1-MG1-EG1 to EG53-MG27-EG53 having the formula EGa-MGb-EGc, or EG1-EG1 to EG53-EG53 having the formula EGa-EGc when MGb is absent, where a is an integer from 1 to 53, b is an integer from 1 to 27, and c is an integer from 1 to 53. The structures of EG1 to EG53 are shown below:

[0357]

[0358]

[0359] The structures of MG1 to MG27 are shown below:

[0360]

[0361] In the MGb structure shown above, two bonding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are marked with numbers for identification purposes.

[0362] In some embodiments, the host may be any one of its N-heterosubstituted variants, its fully or partially deuterated variants, and combinations thereof. In some embodiments, the host has the formula EGa-MGb-Egc and is selected from the group consisting of h1 to h112 defined in the following host group 2 list, where each of MGb, EGa, and Egc is defined as follows:

[0363]

[0364]

[0365] In the above table, the EGa and Egc structures bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with a numerical prefix that identifies their bonding position in the MGb structure.

[0366] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

[0367] In some embodiments, the emissive layer may comprise two hosts: a first host and a second host. In some embodiments, the first host is a hole-transporting host and the second host is an electron-transporting host. In some embodiments, the first host is a hole-transporting host and the second host is a bipolar host. In some embodiments, the first host is an electron-transporting host and the second host is a bipolar host. In some embodiments, the first host and the second host may form an exciplex. In some embodiments, the emissive layer may comprise a third host. In some embodiments, the third host is selected from the group consisting of: an insulating host (wide-bandgap host), a hole-transporting host, and an electron-transporting host. In some embodiments, the third host forms an exciplex with one of the first host and the second host or with both the first host and the second host. In some embodiments, the emissive layer may comprise a fourth host. In some embodiments, the fourth host is selected from the group consisting of: an insulating host (wide-bandgap host), a hole-transporting host, and an electron-transporting host. In some embodiments, the fourth host forms an exciplex with one of the first host, the second host, and the third host, with two of the first host, the second host, and the third host, or with each of the first host, the second host, and the third host. In some embodiments, the LUMO of the electron-transporting host is less than -2.4 eV, less than -2.5 eV, less than -2.6 eV, or less than -2.7 eV. In some embodiments, the HOMO of the hole-transporting host is higher than -5.6 eV, higher than -5.5 eV, higher than -5.4 eV, or higher than -5.35 eV. The HOMO and LUMO values can be determined electrochemically in solution. Cyclic voltammetry and differential pulse voltammetry in solution can be performed using a CH Instruments model 6201B potentiostat, using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Glassy carbon, platinum wire, and silver wire are used as the working electrode, counter electrode, and reference electrode, respectively. The electrochemical potential can be referenced to the internal ferrocene-ferrocenium redox couple (Fc / Fc+) by measuring the peak potential difference by differential pulse voltammetry.According to the literature ((a) Fink R., Heischkel Y., Thelakkat M., Schmidt H.-W., Chem. Mater. 1998, 10, 3620-3625; (b) Pommerehne J., Vestweber H., Guss W., Mahrt R.F., Bassler H., Porsch M., Daub, J. Adv. Mater. 1995, 7, 551), the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies are determined by shifting the cationic and anionic redox potentials relative to the ferrocene reference (4.8 eV relative to vacuum).

[0368] In some embodiments, the compounds as described herein can be a sensitizer or a component of a sensitizer; wherein the device can further comprise an acceptor that receives energy from the sensitizer. In some embodiments, the acceptor is an emitter in the device. In some embodiments, the acceptor can be a fluorescent material. In some embodiments, the compounds as described herein can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain an acceptor in the form of one or more non-delayed fluorescence and / or delayed fluorescence materials. In some embodiments, the compounds as described herein can be used as a component of an exciplex that serves as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer the energy to a final emitter. The acceptor concentration can range from 0.001% to 99.9%. The acceptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a thermally activated delayed fluorescence (TADF) material. In some embodiments, the acceptor is a non-delayed fluorescence material. In some embodiments, the emission can be generated by any one or all of the sensitizer, the acceptor, and the final emitter. In some embodiments, the emission of the acceptor at room temperature has a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM means better color purity for OLED display applications.

[0369] As used herein, phosphorescence generally refers to photon emission when there is a change in the electron spin quantum number, i.e., the initial and final states of the emission have different electron spin quantum numbers, such as from the T1 to the S0 state. Most of the Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, if the exciplex formation involves a triplet emitter, such exciplexes can also emit phosphorescence. On the other hand, fluorescent emitters generally refer to photon emission when the electron spin quantum number remains unchanged, such as from the S1 to the S0 state, or from the D1 to the D0 state. Fluorescent emitters can be either delayed fluorescence or non-delayed fluorescence emitters. Depending on the spin state, fluorescent emitters can be singlet emitters or doublet emitters or other multiplet emitters. It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistical limit through delayed fluorescence. There are two types of delayed fluorescence, namely P-type and E-type delayed fluorescence. P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the thermal population between a triplet and a singlet excited state. Thermal energy can activate the transition of the triplet back to the singlet. This type of delayed fluorescence is also referred to as TADF. E-type delayed fluorescence characteristics can be seen in exciplex systems or single compounds. Without being bound by theory, it is believed that TADF emission requires a compound or exciplex with a small singlet-triplet energy gap (ΔE S-T ) less than or equal to 400, 350, 300, 250, 200, 150, 100, or 50 meV. There are two main types of TADF emitters, one called donor-acceptor type TADF and the other called multi-resonant (MR) TADF. Generally, single compound donor-acceptor TADF compounds are constructed by connecting an electron donor moiety (such as an amino or carbazole derivative) and an electron acceptor moiety (such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). A donor-acceptor exciplex can be formed between a hole transporting compound and an electron transporting compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, MR-TADF materials contain boron, carbon, and nitrogen atoms. Such materials can also contain other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 for delayed fluorescence emission at 293K is less than or equal to 10 microseconds. In some embodiments, such time can be greater than 10 microseconds and less than 100 microseconds.

[0370] In some embodiments, the OLED can include additional compounds selected from the group consisting of: non-delayed fluorescence materials, delayed fluorescence materials, phosphorescent materials, and combinations thereof.

[0371] In some embodiments, the inventive compounds described herein are phosphorescent materials.

[0372] In some embodiments, the phosphorescent material is an emitter that emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material transfers its excited state energy to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer or a component of a sensitizer, and the OLED further includes a receptor. In some embodiments, the phosphorescent material forms an exciplex with another material (such as a host material, an emitter material) within the OLED.

[0373] In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material is an emitter that emits light within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material does not emit light within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material transfers its excited state energy to another material within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material participates in charge transport within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material is a receptor, and the OLED further includes a sensitizer.

[0374] In some embodiments of the OLED, the delayed fluorescence material includes at least one donor group and at least one receptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metal complex. In some embodiments, the delayed fluorescence material is a Pt, Pd, Zn, Cu, Ag, or Au complex (some of which are also referred to as metal-assisted (MA) TADF). In some embodiments, the metal-assisted delayed fluorescence material includes a metal-carbene bond. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material includes at least one chemical group selected from the group consisting of: aryl-amine, aryloxy, arylthio, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borata-naphtho[3,2,1-de]anthracene, 5λ 2 ,9λ 2 -diazabora-naphtho[2,3,4-de]anthracene, 5-oxa-9λ 2-aza-13b-borapicene, azaborinane, oxaborole, acridine, xanthene, dihydrobenzazasilole, dibenzooxasilole, phenoxazine, phenoxathiin, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boranyl, amino, silyl, their aza variants, and combinations thereof. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material comprises tris(aryl / heteroaryl)borane, wherein one or more pairs of substituents from the aryl / heteroaryl are joined to form a ring. In some embodiments, the fluorescent material comprises at least one chemical group selected from the group consisting of naphthalene, anthracene, fluoranthene, phenanthrene, fluorene, pyrene, perylene, and azulene.

[0375] In yet another aspect, the OLEDs of the present disclosure may further comprise an emissive region containing a compound or a formulation of compounds as disclosed in the above compound portions of the present disclosure. In some embodiments, the emissive region may comprise a compound of the formula Ir(L A ) x (L B ) y (L C ) z as defined herein or a formulation of said compound. In some embodiments, the emissive region consists of one or more organic layers, wherein at least one of the one or more organic layers has a minimum thickness selected from the group consisting of 350, 400, 450, 500, 550, 600, 650, and In some embodiments, at least one of the one or more organic layers is formed of an emission system having a figure of merit (FOM) equal to or greater than a value selected from the group consisting of 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. The definition of FOM can be obtained in U.S. Patent Application Publication No. 2023 / 0292605, the entire content of which is incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or a formulation of compounds as disclosed in Part A and Part D of the present disclosure.

[0376] In some embodiments, the OLEDs or emissive regions containing the compounds of the present invention disclosed herein can be incorporated into a full-color pixel arrangement of a device. The full-color pixel arrangement of such a device includes at least one pixel, wherein the at least one pixel includes a first sub-pixel and a second sub-pixel. The first sub-pixel includes a first OLED, and the first OLED includes a first emissive region. The second sub-pixel includes a second OLED, and the second OLED includes a second emissive region. In some embodiments, the first and / or second OLEDs, the first and / or second emissive regions can be the same or different and each can independently have various device features and various embodiments of the compounds of the present invention included therein, as well as various combinations and sub-combinations of various device features and various embodiments of the compounds of the present invention included therein, as disclosed herein.

[0377] In some embodiments, the first emissive region is configured to emit light having a peak wavelength λ max1 ; the second emissive region is configured to emit light having a peak wavelength λ max2 . In some embodiments, the difference between the peak wavelength λ max1 and λ max2 is at least 4 nm but within the same color. For example, light blue and dark blue light as described above. In some embodiments, the first emissive region is configured to emit light having a peak wavelength λ max1 in a region of the visible spectrum of 400 - 500 nm, 500 - 600 nm, 600 - 700 nm; and the second emissive region is configured to emit light having a peak wavelength λ max2 in one of the remaining regions of the visible spectrum of 400 - 500 nm, 500 - 600 nm, 600 - 700 nm. In some embodiments, the first emissive region includes (if more than one) a first number of emissive layers deposited one on top of the other; and the second emissive region includes (if more than one) a second number of emissive layers deposited one on top of the other; and the first number is different from the second number. In some embodiments, both the first emissive region and the second emissive region include phosphorescent materials that can be the same or different. In some embodiments, the first emissive region includes a phosphorescent material, while the second emissive region includes a fluorescent material. In some embodiments, both the first emissive region and the second emissive region include fluorescent materials that can be the same or different.

[0378] In some embodiments, at least one pixel of the OLED or emission region includes a total of N sub-pixels; where the N sub-pixels include a first sub-pixel and a second sub-pixel; where each of the N sub-pixels includes an emission region; and where the total number of emission regions within at least one pixel is equal to or less than N - 1. In some embodiments, the second emission region is identical to the first emission region; and each sub-pixel of at least one pixel includes one emission region identical to the first emission region. In some embodiments, the full-color pixel arrangement may have a plurality of pixels including a first pixel region and a second pixel region; where at least one display characteristic of the first pixel region is different from the corresponding display characteristic of the second pixel region, and where at least one display characteristic is selected from the group consisting of: resolution, cavity mode, color, out-coupling, and color filter.

[0379] In some embodiments, the OLED is a stacked OLED including one or more charge generation layers (CGLs). In some embodiments, the OLED includes a first electrode, a first emission region disposed above the first electrode, a first CGL disposed above the first emission region, a second emission region disposed above the first CGL, and a second electrode disposed above the second emission region. In some embodiments, the first emission region and / or the second emission region may have various device characteristics as described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white light. In some embodiments, one or more of the emission regions in the pixelated OLED or the stacked OLED include a sensitizer and a receptor having various sensitization device characteristics and various embodiments of the inventive compounds disclosed herein. For example, the first emission region is included in the sensitization device while the second emission region is not included in the sensitization device; in some cases, both the first emission region and the second emission region are included in the sensitization device.

[0380] In some embodiments, the OLED can emit light from the plasmon mode with at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% of the light. In some embodiments, at least one of the anode, cathode, or a new layer disposed above the organic emission layer serves as an enhancement layer. The enhancement layer includes a plasmonic material that exhibits surface plasmon resonance, the plasmonic material is non-radiatively coupled to the emitter material, and transfers the excited state energy from the emitter material to the non-radiative mode of the surface plasmon polariton. In some embodiments, the enhancement layer is disposed at a distance from the organic emission layer that does not exceed a threshold distance, where due to the presence of the enhancement layer, the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant. The threshold distance is the position where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. Another threshold distance is the distance at which the total radiative decay rate constant divided by the sum of the total non-radiative decay rate constant and the total radiative decay rate constant is equal to the photoluminescence yield of the emitter material in the absence of the enhancement layer.

[0381] In some embodiments, the OLED further includes an out-coupling layer. In some embodiments, the out-coupling layer is disposed on the side opposite the organic emission layer above the enhancement layer. The out-coupling layer scatters the energy from the surface plasmon polariton. In some embodiments, this energy is scattered as photons into free space. In other embodiments, the energy is scattered from the surface plasmon mode of the device into other modes, such as but not limited to organic waveguide modes, substrate modes, or another waveguide mode. In some embodiments, one or more intermediate layers can be disposed between the enhancement layer and the out-coupling layer. Examples of the intermediate layer can be dielectric materials, including organic, inorganic, perovskite, oxides, and can include stacks and / or mixtures of these materials.

[0382] The enhancement layer changes the effective properties of the medium in which the emitter material resides, thereby causing any one or all of the following: reduced emissivity, changed emission line shape, emission intensity variation with angle, changed emitter material stability, changed OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, anode side, or both sides, or placing the enhancement layer itself as a CGL produces an OLED device that utilizes any of the above effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and shown in the figures, the OLED according to the present disclosure may further include any other functional layers common in OLEDs.

[0383] In some embodiments, the enhancement layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. In some embodiments, the plasmonic material includes at least one metal. In such embodiments, the metal may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, or Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has features of wavelength size arranged periodically, quasi-periodically, or randomly, or features of sub-wavelength size arranged periodically, quasi-periodically, or randomly.

[0384] In some embodiments, the outer coupling layer has features of wavelength size or sub-wavelength size arranged periodically, quasi-periodically, or randomly. In some embodiments, the outer coupling layer may be composed of a plurality of nanoparticles. In some embodiments, the outer coupling layer is composed of a plurality of nanoparticles disposed above a material. In these embodiments, the outer coupling layer can be adjusted by at least one of the following: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, adding an additional layer disposed on the plurality of nanoparticles, changing the thickness of the enhancement layer, or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed from at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outer coupling layer is composed of at least metal nanoparticles, where the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the outer coupling layer is formed by lithography.

[0385] In some embodiments of the plasmonic device, the emitter and / or host compound used in the emission layer has a vertical dipole ratio (VDR) of 0.33 or greater. In some such embodiments, the emitter and / or host compound has a VDR of 0.40, 0.50, 0.60, 0.70, or greater.

[0386] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer may comprise a compound or formulation of compounds as disclosed in the above compound portion of the present disclosure.

[0387] In some embodiments, a consumer product includes an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer can include a compound of formula Ir(L A ) x (L B ) y (L C ) z as defined herein.

[0388] Generally, an OLED includes 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. The injected holes and electrons each migrate toward the electrode of opposite charge. When an electron and a hole are located on the same molecule, an "exciton" is formed, which is a localized electron-hole pair having an excited energy state. When the exciton relaxes via a light-emission mechanism, light is emitted. In some cases, the exciton can be localized as an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur but are generally considered undesirable.

[0389] Figure 1 FIG. 100 shows an organic light-emitting device 100. The figure is not necessarily drawn to scale. Device 100 can include a substrate 110, an anode 115, a hole injection layer (HIL) 120, a hole transport layer (HTL) 125, an electron blocking layer (EBL) 130, an emission layer (EML) 135, a hole blocking layer (HBL) 140, an electron transport layer (ETL) 145, an electron injection layer (EIL) 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by depositing the layers in sequence. The properties and functions of these various layers and example materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated by reference.

[0390] More instances of each of these layers can be obtained. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein 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 herein by reference in its entirety. Examples of light-emitting and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein 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 herein by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety, disclose examples of cathodes that include a composite cathode having a thin layer of metal (such as Mg:Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of the blocking layer are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entirety. Examples of the injection layer are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. A description of the protective layer can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0391] Figure 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. The device 200 can be fabricated by depositing the layers in sequence. Since the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed under the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to the device 100 can be used in the corresponding layers of the device 200. Figure 2 Provides an example of how some of the layers can be omitted from the structure of the device 100.

[0392] Figure 1 and 2The simple layered structure described herein is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure may be used in conjunction with a 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 obtained by combining the various layers described in different ways, or the layers may be completely omitted 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 the various layers as including a single material, it should be understood that combinations of materials may be used, such as a mixture of a host and a dopant, or more generally, mixtures. Additionally, the layers may have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, the hole transport layer 225 transports holes and injects the holes into the 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 such as, for example, those described with respect to Figure 1 and 2 as described.

[0393] Structures and materials not specifically described may also be used, such as OLEDs (PLEDs) comprising polymeric materials, as disclosed, for example, in U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. The OLED structure may deviate from Figure 1 and 2 the simple layered structure described therein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the mesa structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the dimpled structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0394] Unless otherwise specified, any one of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (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) (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, also known as organic vapor jet deposition (OVJD)) (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 other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam deposition. Preferred patterning methods include deposition through a mask, photolithography, and cold welding (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 inkjet and organic vapor jet printing (OVJP). Other methods can also be used. The materials to be deposited can be modified to make them suitable for the specific deposition method. For example, branched or unbranched substituents, preferably containing at least 3 carbons such as alkyl and aryl groups, can be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 or more carbons can be used, and a range of 3 to 20 carbons is preferred. Materials having an asymmetric structure can have better solution processability than materials having a symmetric structure because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents can be used to enhance the ability of small molecules to withstand solution processing.

[0395] Devices fabricated in accordance with embodiments of the present disclosure may further optionally include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage by harmful substances in an environment exposed to, including moisture, vapor, and / or gases. The barrier layer may be deposited on the substrate, on the electrodes, under the substrate, under the electrodes, beside the substrate, beside the electrodes, or on any other part of the device (including the edges). The barrier layer may include 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 and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic compounds or organic compounds or both. Preferred barrier layers include multiple alternating layers of the following materials: polymeric materials and non-polymeric materials; organic materials and inorganic materials; or mixtures of polymeric materials and non-polymeric materials, an example of which is described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098, and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety.

[0396] Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units), which can in turn 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) that can be utilized by end-user product manufacturers, and the like. The electronic component module can optionally include driving electronics and / or a power source. Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more electronic component modules (or units) incorporated therein. Disclosed is a consumer product that includes an OLED that includes a compound of the present disclosure in an organic layer of the OLED. The consumer product should include any kind of product that includes one or more light sources and / or one or more of a certain type of visual display. Some examples of the consumer product include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular telephones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls that include multiple displays tiled together, theater or stadium screens, light therapy devices, and signs. A variety of control mechanisms can be used to control the devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as from 18°C to 30°C, and more preferably at room temperature (20 - 25°C), but can be used outside of this temperature range (e.g., from -40°C to +80°C).

[0397] More details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0398] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0399] In some embodiments, the OLED has one or more characteristics selected from the group consisting of flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further includes a layer comprising carbon nanotubes. In some embodiments, the OLED further includes one or more quantum dots. Such quantum dots can be in the emission layer or in other functional layers, such as a down-conversion layer.

[0400] In some embodiments, the OLED includes an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel with a diagonal less than 10 inches or an area less than 50 square inches. In some embodiments, the OLED is a display panel with a diagonal of at least 10 inches or an area of at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0401] Other materials used in D.OLED

[0402] The materials described herein are various examples of specific layers that can be used in an OLED. It can also be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used by themselves in the emissive dopants in the EML or in combination with a wide variety of other emitters, hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds and devices disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0403] a) Conductive dopants:

[0404] The charge transport layer can be doped with a conductive dopant to generally change its charge carrier density, which in turn will change its conductivity. 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 can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and an n-type conductive dopant is used in the electron transport layer. In some embodiments, the conductive dopant includes at least one chemical moiety selected from the group consisting of cyano, fluorinated aryl or heteroaryl, fluorinated alkyl or cycloalkyl, alkylene, heteroaryl, amide, benzodithiophene, and highly conjugated heteroaryl extended by acyclic double bonds.

[0405] b) HIL / HTL:

[0406] The hole injection / transport materials used in the present disclosure are not particularly limited, and any compound can be used as long as the compound is generally used as a hole injection / transport material. Examples of the materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorohydrocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semi-conductive organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0407] Examples of the aromatic amine derivatives for HIL or HTL include (but are not limited to) the following general structures:

[0408]

[0409] Ar 1 to Ar 9 Each of which is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, fluorene, phenanthrene, fluorene, pyrene, 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, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units, which are the same type or different types of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic ring group. Ar 1 to Ar 9 Each of which may be unsubstituted or may be substituted with a general substituent as described above, and any two substituents may be joined or fused into a ring.

[0410] In some embodiments, each Ar 1 to Ar 9 independently comprises a moiety selected from the group consisting of:

[0411]

[0412] where k is an integer from 1 to 20; X 101 to X 108 is C or N; Z 101 is C, N, O, or S.

[0413] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0414] where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and the coordinating atoms of Y 101 and Y 102 are independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k' + k" is the maximum number of ligands that can be connected to the metal.

[0415] In some embodiments, (Y 101 -Y 102 ) is 2-phenylpyridine or a 2-phenylimidazole derivative. In some embodiments, (Y 101 -Y 102 ) is a carbene ligand. In some embodiments, Met is selected from Ir, Pt, Pd, Os, Cu, and Zn. In some embodiments, the metal complex has a minimum oxidation potential in solution of less than about 0.6 V compared to the Fc + / Fc couple.

[0416] In some embodiments, the HIL / HTL material is selected from the group consisting of: phthalocyanine and porphyrin compounds, starburst triarylamine, CF x fluorohydrocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acids and silane SAMs, triarylamines or polythiophene polymers containing conductive dopants, organic compounds containing conductive inorganic compounds (such as molybdenum oxide and tungsten oxide), n-type semiconducting organic complexes, metal-organic metal complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines containing a spirofluorene core, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indolocarbazole, isoindole compounds, and metal carbene complexes.

[0417] c) EBL:

[0418] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Additionally, a blocking layer can be used to confine emission to a desired region of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or higher triplet energy compared to one or more emitters closest to the EBL interface. In some embodiments, the compound used in the EBL contains at least one carbazole group and / or at least one arylamine group. In some embodiments, the HOMO level of the compound used in the EBL is shallower than the HOMO level of one or more of the hosts in the EML. In some embodiments, the compound used in the EBL contains the same molecule or the same functional group as one of the hosts described below.

[0419] d) Host:

[0420] The light-emitting layer of the organic EL device of the present disclosure preferably contains at least a light-emitting material as a dopant and a host material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used as long as the host does not completely quench the emission of the dopant.

[0421] Examples of the metal complex used as the host preferably have the following general formula:

[0422]

[0423] wherein Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, and the coordinating atoms of Y 103 and Y 104 are independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0424] In some embodiments, the metal complex is:

[0425]

[0426] wherein (O-N) is a bidentate ligand having a metal coordinated to the O and N atoms.

[0427] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0428] In some embodiments, the host compound contains at least one selected from the following groups: the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, chrysene, phenanthrene, fluorene, pyrene, 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, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-carbazole, aza-indolocarbazole, aza-triphenylene, aza-tetraphenylene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borata-naphtho[3,2,1-de]anthracene; and the group consisting of 2 to 10 cyclic structural units, the cyclic structural units being the same type or different types of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option within each group may be unsubstituted or may be substituted with a general substituent as described herein or may be further fused.

[0429] In some embodiments, the host compound contains at least one selected from the moieties consisting of the following:

[0430] where k is an integer from 0 to 20 or from 1 to 20. X 101 to X 108 are independently selected from C or N. Z 101 and Z 102 are independently selected from C, N, O, or S.

[0431] In some embodiments, the host material is selected from the group consisting of arylcarbazole, metal 8-hydroxyquinolinates (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, based on Compounds, aryltriphenylene compounds, polycondensed heteroaryl compounds, donor-acceptor type molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., pvk), spirofluorene compounds, spirofluorene-carbazole compounds, indolocarbazole, 5-membered ring electron-deficient heterocycles (e.g., triazole, oxadiazole), tetracene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al containing N^N ligands), dibenzothiophene / dibenzofuran-carbazole compounds, silicon / germanium aryl compounds, aryl benzoyl esters, carbazole linked by non-conjugated groups, azacarbazole / dibenzofuran / dibenzothiophene compounds, and high triplet metal organometallic complexes (e.g., metal-carbene complexes).

[0432] e) Emitter materials in the EML:

[0433] One or more emitter materials can be used in combination with the compounds or devices of the present disclosure. The emitter materials can be emissive or non-emissive in the current devices as described herein. Examples of emitter materials are not particularly limited, and any compound can be used as long as the compound can generate emission in a conventional OLED device. Examples of suitable emitter materials include, but are not limited to, compounds capable of generating emission via phosphorescence, non-delayed fluorescence, delayed fluorescence (especially thermally activated delayed fluorescence, i.e., TADF (also known as E-type delayed fluorescence)), triplet-triplet annihilation, or a combination of these methods.

[0434] In some embodiments, the emitter material has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0435] where L 1 , L 2 and L 3 can be the same or different;

[0436] where x is 1, 2 or 3;

[0437] where y is 0, 1 or 2;

[0438] where z is 0, 1 or 2;

[0439] where x + y + z is the oxidation state of the metal M;

[0440] where L 1 is selected from the group consisting of the structures in the following ligand list:

[0441]

[0442]

[0443]

[0444] where each L 2 and L 3 is independently selected from the group consisting of and the structures in the ligand list; wherein:

[0445] M is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;

[0446] T is selected from the group consisting of: B, Al, Ga, and In;

[0447] K 1 ' is a direct bond or is selected from the group consisting of NR e 、PR e 、O, S, and Se;

[0448] Each Y 1 to Y 15 is independently selected from the group consisting of carbon and nitrogen;

[0449] Y' is selected from the group consisting of BR e 、NR e 、PR e 、O, S, Se, C=O, S=O, SO2, CR e R f 、SiR e R f and GeR e R f ;

[0450] Each R a 、R b 、R c and R d can independently represent mono-substituted to the maximum possible number of substitutions or unsubstituted;

[0451] Each R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R f is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; and

[0452] Any two of these substituents may be fused or joined to form a ring or form a multidentate ligand.

[0453] In some embodiments, the emitter material is selected from the group consisting of dopant group 1:

[0454]

[0455]

[0456]

[0457]

[0458] where

[0459] X 96 to X 99 each is independently C or N;

[0460] each Y 100 is independently selected from the group consisting of NR″, O, S, and Se;

[0461] R 10a 、R 20a 、R 30a 、R 40a and R 50a each independently represents mono-substituted, up to maximally substituted, or unsubstituted;

[0462] R, R', R″, R 10a 、R 11a 、R 12a 、R 13a 、R 20a 、R 30a 、R 40a 、R 50a 、R 60 、R 70 、R 97 、R 98 and R 99 each is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; any two substituents may be joined or fused to form a ring.

[0463] In some embodiments, the emitter material is selected from the group consisting of dopant group 2:

[0464]

[0465]

[0466]

[0467]

[0468]

[0469] Wherein:

[0470] Each Y 100 is independently selected from the group consisting of NR″, O, S, and Se;

[0471] L is independently selected from the group consisting of: a direct bond, BR″, BR″R″′, NR″, PR″, O, S, Se, C═O, C═S, C═Se, C═NR″, C═CR″R″′, S═O, SO2, CR″, CR″R″′, SiR″R″′, GeR″R″′, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0472] X 100 and X 200 are each independently selected, at each occurrence, from the group consisting of O, S, Se, NR″, and CR″R″′;

[0473] Each R A” 、R B” 、R C” 、R D” 、R E” 、R F” independently represents mono-substituted, up to maximally substituted, or unsubstituted;

[0474] R, R′, R″, R″′, R A1' 、R A2' 、R A” 、R B” 、R C” 、R D” 、R E” 、R F” 、R G” 、R H” 、R I” 、R J” 、R K” 、R L” 、R M” and R N” each independently is hydrogen or a substituent selected from the group consisting of common substituents as defined herein; and any two substituents may be joined or fused to form a ring.

[0475] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom may be replaced by N to form a heterocycle. In some embodiments, the maximum number of N atoms in a ring is 1 or 2. In some embodiments of the above dopant group 2, the Pt atom in each formula may be replaced by a Pd atom.

[0476] In some embodiments of the OLED, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metal complex. In some embodiments, the delayed fluorescence material is a Zn, Cu, Ag or Au complex.

[0477] In some embodiments of the OLED, the delayed fluorescence material has the formula M(L 5 )(L 6 ), where M is Cu, Ag or Au, and L 5 and L 6 are different, and L 5 and L 6 are independently selected from the group consisting of:

[0478]

[0479] where A 1 -A 9 are each independently selected from C or N;

[0480] Each R P , R Q and R U independently represents mono-substituted, up to maximum substitution or unsubstituted;

[0481] where each R P , R P , R U , R SA , R SB , R RA , R RB , R RC , R RD , R RE and R RF are independently hydrogen or a substituent selected from the group of general substituents as defined herein; any two substituents may be joined or fused to form a ring.

[0482] In some embodiments of the OLED, the delayed fluorescence material comprises at least one selected from the group of donor moieties consisting of:

[0483]

[0484] wherein Y T , Y U , Y V and Y W are each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO2.

[0485] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures up to a total of at most three carbon ring atoms together with its substituents can be replaced by N.

[0486] In some embodiments, the delayed fluorescence material comprises at least one of acceptor moieties selected from the group consisting of: nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moiety and the donor moiety as described herein can be directly linked, linked via a conjugated linking group or a non-conjugated linking group (such as sp 3 carbon or silicon atoms).

[0487] In some embodiments, the fluorescent material comprises at least one of chemical moieties selected from the group consisting of:

[0488]

[0489]

[0490] wherein Y F , Y G , Y H and Y I are each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO2;

[0491] wherein X F and X G are each independently selected from the group consisting of C and N.

[0492] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures up to a total of at most three carbon ring atoms together with its substituents can be replaced by N.

[0493] f) HBL:

[0494] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emissive layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to a desired region of the OLED. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and / or a higher triplet energy compared to one or more of the emitters closest to the HBL interface.

[0495] In some embodiments, the compound used in the HBL contains the same molecule or the same functional groups as those used in the host described above.

[0496] In some embodiments, the compound used in the HBL comprises at least one of the following moieties selected from the group consisting of:

[0497] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0498] g) ETL:

[0499] The electron transport layer (ETL) can include materials capable of transporting electrons. The electron transport layer can be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound can be used as long as it is commonly used to transport electrons.

[0500] In some embodiments, the compound used in the ETL contains at least one of the following moieties in the molecule:

[0501] and fullerenes; where k is an integer from 1 to 20, X 101 to X 108 is selected from C or N; Z 101 is selected from the group consisting of C, N, O, and S.

[0502] In some embodiments, the metal complex used in the ETL contains, but is not limited to, the following general formula:

[0503]

[0504] where (O-N) or (N-N) is a bidentate ligand having a metal coordinated to the atoms O, N, or N,N; L 101 is another ligand; and k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0505] In some embodiments, the ETL material is selected from the group consisting of: anthracene - benzimidazole compounds, azatriphenylene derivatives, anthracene - benzothiazole compounds, metal 8 - hydroxyquinolinates, metal hydroxybenzoquinolinates, bathocuprine compounds, 5 - membered ring electron - deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzimidazole), silole compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N^N) complexes.

[0506] h) Charge - generating layer (CGL)

[0507] In a tandem or stacked OLED, the CGL plays a fundamental role in performance and consists of an n - doped layer and a p - doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrodes. The electrons and holes consumed in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include the n - and p - conductivity dopants used in the transport layer.

[0508] In any of the compounds disclosed herein, the hydrogen atoms can be partially or fully deuterated. The minimum amount of deuterated hydrogen in the compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, the deuteration percentage has its ordinary meaning and includes the percentage of all possible hydrogen and deuterium atoms replaced by deuterium atoms. In some embodiments, the deuterium atoms are attached to an aromatic ring. In some embodiments, the deuterium atoms are attached to a saturated carbon atom, such as an alkyl or cycloalkyl carbon atom. In some other embodiments, the deuterium atoms are attached to a heteroatom, such as a Si or Ge atom.

[0509] It should be 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 can be replaced by other materials and structures without departing from the spirit of the invention. The invention as claimed may thus include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories as to why the invention works are not intended to be limiting.

[0510] Experimental data

[0511] Synthesis of Invention Example 1

[0512]

[0513] Scheme:

[0514]

[0515] Step 1:

[0516]

[0517] Place 7-bromo-5,9-dioxa-13b-boraperylene[3,2,1-de]anthracene (1, 2 g, 5.73 mmol, 1 eq) into a 250 mL two-necked round-bottom flask equipped with a rubber septum and a magnetic stir bar. Evacuate the flask with 1 for 10 minutes under vacuum and then backfill with nitrogen. Add anhydrous DCM (150 mL) thereto. Cool the suspension to 0 °C in an ice bath. Add nitronium tetrafluoroborate (3.044 g, 22.92 mmol, 4 eq) to the suspension in one portion, and stir the mixture at 0 °C for an additional 1 hour. Then remove the ice bath and allow the reaction mixture to warm to room temperature and stir overnight. The reaction mixture changes from colorless to purple over time. After stirring overnight, concentrate the reaction mixture under vacuum and neutralize with saturated aqueous NaHCO3 (50 mL). Then extract the aqueous phase with DCM (3 × 100 mL). Dry the combined organic matters over anhydrous sodium sulfate, filter and concentrate under vacuum at 50 °C to obtain an off-white solid. Purify the crude material by column chromatography, eluting with DCM and heptane, to obtain 2 as a white solid, 1 g (35% yield).

[0518] Step 2

[0519]

[0520] Charge 7-bromo-6-nitro-5,9-dioxa-13b-boraperylene[3,2,1-de]anthracene 2 (0.355 g, 0.90 mmol, 1 eq), 3-(tert-butyl)aniline (0.202 g, 1.35 mmol, 1.5 eq), cesium carbonate (0.734 g, 2.25 mmol, 2.5 eq) and Sphos (0.74 g, 0.18 mmol, 0.2 eq) into a flame-dried 48 mL round-bottom pressure vessel equipped with a magnetic stir bar. Evacuate the pressure vessel containing the solid reagents for 5 minutes under vacuum and then backfill with nitrogen. Add anhydrous toluene (15 mL), and purge the solution with nitrogen for 15 minutes. Add tris(dibenzylideneacetone)dipalladium(0) (0.082 g, 0.90 mmol, 10 mol%) thereto, heat the reaction mixture to 90 °C and stir at the same temperature overnight. After cooling to room temperature, dilute the mixture with DCM (10 mL), filter through a Celite plug and wash with DCM (20 mL). Concentrate the combined organic extracts, dissolve the resulting residue in a small amount of DCM, and then add silica gel. After drying, purify the solid material by column chromatography, eluting with EtOAc / heptane, to obtain 3 as a red oil, 0.11 g (26% isolated yield).

[0521] Step 3

[0522]

[0523] Transfer N-(3-(tert-butyl)phenyl)-6-nitro-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-7-amine 3 (0.11 g, 0.238 mmol, 1 eq) to a 100 mL two-neck round-bottom flask with EtOH (5 mL), then add hydrazine monohydrate (0.417 g, 8.33 mmol, 35 eq), and 10% wet Pd / C (containing 55% water) (0.01 g, 0.095 mmol, 0.4 eq). Then reflux the resulting solution for 2 h. Cool the reaction mixture to room temperature, dilute with DCM (20 mL), filter through a Celite plug and wash with DCM (20 mL). Concentrate and dry the combined organic extracts under vacuum to give 4. Crude yield: 0.055 g (53%). This compound was used in the next step without further purification.

[0524] Step 4

[0525]

[0526] Transfer N7-(3-(tert-butyl)phenyl)-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene-6,7-diamine 4 (0.055 g, 0.13 mmol, 1 eq) to a 50 mL round-bottom flask with triethyl orthoformate (5 mL, 0.075 g, 0.51 mmol, 4 eq). Add p-toluenesulfonic acid (0.0055 g, 0.032 mmol, 0.25 eq) thereto and stir the solution at room temperature overnight. All starting materials were consumed within 2 h. Neutralize the reaction mixture with saturated aqueous NaHCO3 (10 mL). Extract the aqueous phase with EtOAc (3 × 100 mL). Wash the combined organic extracts with brine, dry over Na2SO4, concentrate and dry under vacuum to give 5, 45 mg (81% yield). This product was used in the next step without further purification.

[0527] Step 5

[0528]

[0529] 11-(3-(tert-Butyl)phenyl)-11H-9,14-dioxa-11,13-diaza-4b-borata-anthra[3,2,1-de]naphthalene 5 (0.045 mg, 0.10 mmol, 1 eq) was transferred to a pressure vessel with acetonitrile (5 mL). Methyl iodide (0.022 mg, 0.15 mmol, 9.5 μL) was added dropwise thereto, and the resulting solution was heated overnight at 80 °C (in a preheated oil bath). After cooling to room temperature, the reaction mixture was diluted with DCM (10 mL). It was further washed with an aqueous saline solution, and the organic phase was extracted with more DCM (3 × 40 mL). The combined organic extracts were dried over Na2SO4, concentrated, and dried under vacuum to give 6, 24 mg (62% yield).

[0530] Step 6

[0531]

[0532] Example 1 of the present invention can also be prepared by following the literature procedure (Dalton Trans., 2008, 916 - 923).

[0533] Synthesis of Example 2 of the present invention

[0534]

[0535] Flowchart

[0536]

[0537] Step 1

[0538]

[0539] Potassium carbonate (199 g, 2.0 eq, 1.44 mol) and iodomethane (205 g, 90 mL, 2.0 eq, 1.44 mol) were added to a solution of 2-bromo-4-fluoro-5-nitrophenol 1 (170. g, 1.0 eq, 720 mmol) in acetone (1.75 L), and the mixture was heated overnight at 50 °C in an oil bath with a condenser. The reaction mixture was cooled and the acetone was evaporated. The residue was dissolved in EtOAc (1 L) and water (1 L), and the layers were separated. The organic layer was washed with water (300 mL), dried (MgSO4), filtered and evaporated to give the crude material 2. The crude material was filtered through silica gel (2 L) in a sintered glass funnel, charged with a small amount of DCM and eluted with heptane, then eluted with 25%, and subsequently 50% DCM / heptane. The product eluates were combined and evaporated to give 170 g of 2 as a pale yellow powder. The solid was dissolved in hot EtOAc (85 mL), hexane (600 mL) was added, and the mixture was cooled in an ice bath. The precipitate was filtered and washed with cold hexane to give 156 g (86%) of 2 as yellow needles.

[0540] Step 2

[0541]

[0542] Sodium bicarbonate (94.8 g, 3.0 eq, 1.13 mol) and 1-bromo-5-fluoro-2-methoxy-4-nitrobenzene 2 (94.0 g, 1 eq, 376.mmol) were added to a solution of aniline (105.0 g, 103.0 mL, 3.0 eq, 1.13 mol) in DMSO (370 mL), and the mixture was heated overnight at 110 °C in an oil bath with a condenser. The reaction mixture was cooled and poured into EtOAc (4 L) and water (2 L), and transferred using EtOAc and water. The reaction mixture was stirred until dissolved. The layers were separated, the EtOAc layer was washed with water (4 × 1 L), dried (MgSO4), filtered and evaporated to give the crude material 3, which was recrystallized by dissolving in hot EtOAc (3 mL per gram of crude material 3), and then adding warm heptane (3 volumes relative to EtOAc). The mixture was then cooled to room temperature and then in an ice bath. The mixture was filtered and washed with heptane to give 88.7 g (73%) of 3 as red / orange needles.

[0543] Step 3

[0544]

[0545] Iron (48.7 g, 10.0 eq, 873 mmol), ammonium chloride (46.7 g, 10.0 eq, 873 mmol), and water (382 mL) were added to a solution of 5-bromo-4-methoxy-2-nitro-N-phenylaniline 3 (28.2 g, 1 eq, 87.3 mmol) in absolute ethanol (380 mL). The mixture was then heated in an oil bath at 75 °C for 3 h. The reaction mixture was cooled, diluted with absolute ethanol (300 mL), and filtered through a bed of diatomaceous earth in a sintered glass funnel (filtration was slow, so a large-diameter funnel was used to obtain a large surface area). The bed was then washed with THF (300 mL). The filtrate was evaporated (most of the ethanol and THF were removed) to give a dark aqueous mixture. This was dissolved in EtOAc (400 mL) and water (100 mL). The layers were separated, and the EtOAc layer was dried (MgSO4), filtered, and evaporated to give 25 g (100%) of crude material 4 as a dark oil. This material was used as such without further purification.

[0546] Step 4

[0547]

[0548] p-Toluenesulfonic acid monohydrate (1.95 g, 0.10 eq, 10.2 mmol) was added to a solution of 5-bromo-4-methoxy-N1-phenylbenzene-1,2-diamine 4 (30.0 g, 1 eq, 102 mmol) in trimethyl orthoformate (500 mL, 45 eq, 4.6 mol). The resulting solution was then heated in an oil bath at 95 °C for 3 h. The reaction mixture was cooled and evaporated to give crude material 5 as a dark gummy oil. The crude material 5 was dissolved in a small amount of DCM and filtered through a silica gel bed (1 L) in a sintered glass funnel, eluting with 10%-15% EtOAc / DCM. The eluate containing 5 was evaporated to give a gummy material. Ether (2 mL / g of crude material) was added to the reaction mixture, and the mixture was stirred overnight. The solid was filtered and washed with ether to give 19.8 g (64%) of 5 as a light pink solid.

[0549] Step 5

[0550]

[0551] A solution of 6-bromo-5-methoxy-1-phenyl-1H-benzo[d]imidazole 5 (0.220 g, 1 eq, 726 μmol) in anhydrous EtOH (6.0 mL), toluene (1.6 mL), and 2 M aqueous K2CO3 (0.91 μL, 2.5 Eq, 1.82 mmol) was degassed for 15 minutes. (4-Chloro-2-fluorophenyl)boronic acid (215 mg, 1.7 eq, 1.23 mmol) and Pd(PPh3)4 (42 mg, 0.050 eq, 36 μmol) were added to the solution, the headspace was purged with nitrogen, and then the mixture was heated overnight in an oil bath at 65 °C. The reaction mixture was cooled and diluted with EtOAc (50 mL) and water (10 mL). The layers were separated, and the organic layer was washed with water (10 mL) and brine (10 mL), then dried, filtered, and evaporated to give crude material 6. 6 was purified by column chromatography (0 to 70% DCM / heptane) to give 178 mg (69%) of 6 as a yellow solid.

[0552] Step 6

[0553]

[0554] In a dry ice-acetone bath, boron tribromide (223 μL, 3.0 eq, 2.36 mmol) was slowly added to a solution of 6-(4-chloro-2-fluorophenyl)-5-methoxy-1-phenyl-1H-benzo[d]imidazole 6 (277.0 mg, 1 eq, 785 μmol) in DCM (2.5 mL). The solution was warmed to room temperature over 2.5 h. The reaction mixture was slowly poured onto ice and then basified by the addition of saturated aqueous NaHCO3. EtOAc (50 mL) was added and the layers were separated. The organic layer was washed with water (10 mL), then dried, filtered, and evaporated to give 208 mg (78%) of crude material 7. This material was used as such without further purification.

[0555] Step 7

[0556]

[0557] K2CO3 (245 mg, 3.0 eq, 1.77 mmol) was added to a solution of 6-(4-chloro-2-fluorophenyl)-1-phenyl-1H-benzo[d]imidazol-5-ol (200. mg, 1 eq, 590 μmol) in NMP (3.13 mL). Subsequently, the resulting mixture was heated overnight in an oil bath at 160 °C. The reaction mixture was cooled and dissolved in EtOAc (30 mL) and water (10 mL). The layers were separated, and the aqueous layer was extracted with EtOAc (10 mL). The combined organic layers were washed with water (10 mL), dried (MgSO4), filtered, and evaporated to give the crude material 8. Column chromatography of 8 (loaded with DCM and eluted with 0 to 30% EtOAc / DCM) gave 8 as a pale yellow solid (120 mg, 63%).

[0558] Step 8

[0559]

[0560] Compound 9 can be prepared by following the literature procedure (Angew. Chem. Int. Ed. 2013, 52, 10035 - 10039).

[0561] Step 9

[0562]

[0563] Compound 10 can be prepared by using the procedure for Compound 1 of the present invention (Step 5).

[0564] Step 10

[0565]

[0566] Example 2 of the present invention can be prepared by following the literature procedure (Dalton Trans. 2008, 916 - 923).

[0567] Calculation results *

[0568]

[0569]

[0570]

[0571]

[0572]

[0573] Calculations were performed using the B3LYP functional with the CEP-31G basis set. Geometric structure optimizations were carried out in vacuo. The excitation energies of these optimized geometric structures were obtained using time-dependent density functional theory (TDDFT). A continuum solvent model was applied in the TDDFT calculations to simulate the tetrahydrofuran solvent. All calculations were performed using the Gaussian program.

[0574] The calculated values obtained using the DFT functional sets and basis sets identified above are theoretical values. Computational composite protocols (such as Gaussian with the CEP-31G basis set as used herein) rely on the assumption that electronic effects are additive and can thus be extrapolated to the complete basis set (CBS) limit using a larger basis set. However, when the goal of the study is to understand the variations in HOMO, LUMO, S1, T1, bond dissociation energies, etc. for a series of structurally related compounds, additive effects are expected to be similar. Thus, although the absolute error using B3LYP may be significant compared to other computational methods, the relative differences between the HOMO, LUMO, S1, T1, and bond dissociation energy values calculated using the B3LYP protocol are expected to reproduce experiments well. See, e.g., Hong et al., Chem. Mater. 2016, 28, 5791-98, 5792-93 and Supplementary Information (discussing the reliability of DFT calculation results in the case of OLED materials). In addition, with respect to iridium or platinum complexes applicable in the OLED field, the data obtained from DFT calculations are closely related to actual experimental data. See Tavasli et al., J. Mater. Chem. 2012, 22, 6419-29, 6422 (Table 3) (showing DFT calculations closely related to actual data for a variety of emissive complexes); G. R. Morello, J. Mol. Model. 2017, 23:174 (studying various DFT functional sets and basis sets and inferring that the combination of B3LYP and CEP-31G is particularly accurate for emissive complexes).

[0575] The calculation results show that the compounds of the present invention have an emission curve of 447 nm to 517 nm; it is suitable for green and blue OLED applications.

Claims

1. A compound comprising formula Ir(L A ) x (L B ) y (L C ) z The structure of which: x is 1, 2, or 3; y and z are each independently 0, 1 or 2; x+y+z=3; The first ligand L A Containing the structure of Formula I: L B and L C Each of L is independently a bidentate ligand, and L B and L C different; Moiety A is a polycyclic fused ring system comprising at least three rings, wherein each ring of the polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; The portion A comprises at least one non-benzene ring; Moiety B is a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; X 1 , X 2 and Z 1 Each of is independently C or N; Ir-C 1 The bond is a metal-carbene bond; Y' is selected from the group consisting of: BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR' and GeRR'; L 1 Selected from the group consisting of: direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR' and GeRR'; K 1 Selected from the group consisting of: direct key, O, S, N(R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β ); R A and R B Each independently represents mono-substitution to the maximum permissible substitution or no substitution; Each R, R', R α , R β , R A and R B are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; Any two substituents can be joined or fused to form a ring; and L A , L B or L C Two or more of R can join to form a tetradentate or hexadentate ligand, provided that if moiety B is a benzene ring and moiety A contains three rings, then at least one R A is selected from the group consisting of an electron withdrawing group, a silane group and a germane group, or the moiety A comprises at least one nitrogen ring atom.

2. The compound according to claim 1, wherein each of R, R', R α , R β , R A and R B are independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

3. The compound of claim 1, wherein moiety B is independently selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza- benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene and aza-fluorene; and / or wherein the moiety A has 3 rings and is selected from the group consisting of carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene and aza-fluorene; and / or wherein part A comprises and contains Y'-C 1 -X 1 The first moiety A1 is fused to a ring of , and the moiety A1 is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzobenzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, aza-phenanthrene, aza-anthracene, phenanthridine, fluorene and aza-fluorene.

4. The compound according to claim 1, wherein x is 3; and / or wherein K 1 is a direct bond; and / or wherein Y' is selected from the group consisting of BR, NR and PR; and / or wherein L 1 It is a direct key.

5. The compound of claim 1, wherein the electron withdrawing group is selected from the group consisting of: F, CF3, CN, COCH3, CHO, COCF3, COOME, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R K2 )3、(R K2 )2CCN、(R K2 )2CCF3, CNC(CF3)2, BR K3 R K2 , substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, Each R k1 represents mono-substitution to the maximum permissible substitution or no substitution; where Y G Select from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f , and GeR e R f' ;and Where R k1 , R k2 , R k3 , R e and R f Each of the above is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiol, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

6. The compound according to claim 1, wherein at least one R A A substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, a silane group, a germane group, an electron withdrawing group, and combinations thereof is included.

7. The compound of claim 1, wherein at least one RA on the last or penultimate ring of moiety A comprises an electron withdrawing group.

8. The compound according to claim 1, wherein at least one R A Selected from the group consisting of an electron withdrawing group, a silane group and a germane group.

9. The compound according to claim 1, wherein the ligand L A Select from the group consisting of: in: X 3 To X 37 Each and every occurrence of X in is independently C or N; each Y A1 , Y A2 , Y A3 and Y B Independently selected from the group consisting of: BR e NR e , PR e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f and GeR e R f ; R A ' and R B Each of ' independently represents a single substitution to the maximum possible number of substitutions or no substitution; Each R e , R f , R A '、R B ' and R N is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; And any two substituents can be joined or fused to form a ring.

10. The compound according to claim 1, wherein the ligand L A Select from the group consisting of: in: X 3 To X 37 Each and every occurrence of X in is independently C or N; Y A1 , Y A2 , Y A3 , Y A4 and Y B Each of which is independently selected from the group consisting of: BR e , NR e 、PR e 、O, S, Se, C=O, S=O, SO2, CR e R f 、SiR e R f 和GeR e R f ; R A ' and R B Each of ' independently represents a single substitution to the maximum possible number of substitutions or no substitution; Each R e , R f , R A '、R B ' and R N is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; and Any two substituents can be joined or fused to form a ring.

11. The compound according to claim 1, wherein the ligand L A Choose from L Ai A group consisting of, wherein i is an integer from 1 to 179; wherein L A1 To L A179 Each of is defined as follows:

12. The compound according to claim 1, wherein L B and L C Each independently selected from the group consisting of: in: T is selected from the group consisting of B, Al, Ga and In; K 1 'Selected from the group consisting of: single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ; Y 1 To Y 13 Each of which is independently selected from the group consisting of C and N; Y'Select from the group consisting of: BR e , BR e R f NR e , PR e 、P(O)R e 、O、S、Se、 C=O, C=S, C=Se, C=NR e , C=CR e R f , S=O, SO2, CR e R f , SiR e R f , and GeR e R f ; R e and R f capable of being fused or joined to form a ring; Each R a , R b , R c and R d independently represents monosubstituted to the maximum allowed number of substitutions or no substitution; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiol, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two substituents in can be fused or joined to form a ring or to form a multidentate ligand.

13. The compound of claim 1, wherein the compound is selected from the group consisting of:

14. An organic light-emitting device, comprising: anode; a cathode; and An organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound of claim 1.

15. A consumer product comprising an organic light-emitting device, the organic light-emitting device comprising: anode; a cathode; and An organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound of claim 1.

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