Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. The present disclosure provides a compound having the formula Ir (LA) x (LB) y (Lc) z or Ir (LA ") p (LB) q (LC) r, where: LA has the structure of formula IA: # imgabs0 # LA" comprises the structure of formula III: # imgabs1 # LB has the structure of formula IB: # imgabs2 # LC is a bidentate ligand, and the structure of formula II # imgabs3 is fused with at least one of the moieties A, B, C, D or ring H. Also provided are formulations, OLEDs and consumer products containing the compounds.

Description

[0001] Cross - Reference to Related Applications

[0002] This application is a partial continuation of U.S. Patent Application No. 18 / 814,301, filed on August 23, 2024, the entire content of which is incorporated herein by reference. This application also claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 63 / 664,204, filed on June 26, 2024, U.S. Provisional Application No. 63 / 562,444, filed on March 7, 2024, U.S. Provisional Application No. 63 / 625,704, filed on January 26, 2024, U.S. Provisional Application No. 63 / 620,548, filed on January 12, 2024, and U.S. Provisional Application No. 63 / 614,955, filed on December 27, 2023, the entire content of each 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 transport agents, or exciton transport agents in devices such as organic light-emitting diodes and related electronic devices and consumer products. Background Art

[0004] For various reasons, optoelectronic devices utilizing 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 also be used for OLEDs. White OLEDs can be single-emission 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 having the formula Ir(L A ) x (L B ) y (Lc) z ,

[0008] wherein:

[0009] L A has the structure of Formula IA:

[0010] L B has the structure of Formula IB:

[0011] L C is a bidentate ligand;

[0012] x is 1 or 2; y is 1 or 2; z is 0 or 1; and x + y + z = 3;

[0013] the structure of Formula II is fused to at least one of moieties A, B, C or D;

[0014] Each of W 1 to W 8 is independently C or N;

[0015] Each of moiety A, moiety B, moiety C and moiety D is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5 - to 10 - membered carbocyclic or heterocyclic ring;

[0016] n is 1, 2 or 3;

[0017] The dashed line in Formula II represents a direct bond to two adjacent carbon atoms;

[0018] Each of R A’ , R B’ , R C’ , R D’ and R E independently represents mono - substitution to the maximum allowable substitution or no substitution;

[0019] Each R A’ , R B’ , R C’ , R D’ and R Eindependently is 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, selenyl and combinations thereof; and

[0020] any two substituents may be fused or joined to form a ring.

[0021] In another aspect, the present disclosure provides an Ir complex having a ligand L comprising Structure III A” ; wherein:

[0022] moiety F 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;

[0023] X 1 to X 10 each independently is C or N;

[0024] Y A 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’;

[0025] Structure III comprises Structure II which is fused to Ring H or Ring G; n is 1, 2 or 3;

[0026] the dashed line in Structure II represents a direct bond to two adjacent carbon atoms;

[0027] R E , R F , R G and R H each independently represents mono-substituted to maximum allowable substitution or no substitution;

[0028] wherein each R, R’, R E , R F , R G and R HIndependently is 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, selenyl, and combinations thereof;

[0029] Wherein any two substituents may be fused or joined to form a ring.

[0030] In another aspect, the present disclosure provides a formulation comprising a compound having the formula Ir(L A ) x (L B ) y (Lc) z as described herein.

[0031] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound having the formula Ir(L A ) x (L B ) y (Lc) z as described herein.

[0032] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer, the organic layer comprising a compound having the formula Ir(L A ) x (L B ) y (Lc) z as described herein.

[0033] In another aspect, the present disclosure provides a formulation comprising a compound having a ligand L having a structure of Formula III as described herein. A” as described herein.

[0034] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound having a ligand L having a structure of Formula III as described herein. A” as described herein.

[0035] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer, the organic layer comprising a compound having a ligand L having a structure of Formula III as described herein. A” as described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 Shows an organic light emitting device.

[0037] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is shown. Detailed implementation

[0038] A. Terms

[0039] Unless otherwise specified, the following terms used herein are defined as follows:

[0040] As used herein, "top" means farthest from the substrate, and "bottom" means closest to the substrate. When 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 if there are various organic layers between the cathode and the anode, the cathode can still be described as being "disposed on" the anode "above".

[0041] As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in a liquid medium in the form of a solution or suspension and / or deposited from a liquid medium.

[0042] As used herein, and as is generally understood by those skilled in the art, if the 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" the 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.

[0043] As used herein, and as is generally understood by those skilled 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 the work function is usually measured as a negative number relative to the vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram where the top is the vacuum level, a "higher" work function is shown as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO energy levels follow different rules from those of the work function.

[0044] This document can describe layers, materials, regions, and devices in reference to the color of the light they emit. Generally speaking, as used herein, an emission region described as producing a specific color of light can include one or more emission layers arranged in a stacked manner above one another.

[0045] As used herein, "NIR", "red", "green", "blue", "yellow" layers, materials, regions, or devices refer to layers, materials, regions, or devices that emit light in the wavelength ranges of approximately 700 - 1500 nm, 580 - 700 nm, 500 - 600 nm, 400 - 500 nm, 540 - 600 nm, respectively, or layers, materials, regions, or devices that have the highest emission spectral peak within the corresponding wavelength regions. In some arrangements, separate regions, layers, materials, or devices can 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 the "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, but these ranges can vary for some configurations.

[0046] In some arrangements, a color-changing layer is provided that converts, modifies, or changes the color of the light emitted by another layer into an emission with a different wavelength. This color-changing layer can 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 speaking, 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 can be a "red" filter to filter the input light to remove light with wavelengths outside the range of approximately 580 - 700 nm. A "component" of "color" refers to a component that, when activated or used, produces or otherwise emits light with a specific 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.

[0047] As used herein, based on the light initially generated by a material, layer, or region being opposite to the light ultimately emitted by the same or a different structure, 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 leads to 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 if the sub-pixel is a "red" or "green" component.

[0048] 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:

[0049]

[0050] The terms "halo", "halogen", and "halo group" can be used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0051] The term "acyl group" refers to a substituted carbonyl group (-C(O)-R s ).

[0052] The term "ester" refers to a substituted oxycarbonyl group (-O-C(O)-R s or -C(O)-O-R s ).

[0053] The term "ether" refers to an -OR s group.

[0054] The terms "sulfanyl" or "thioether" can be used interchangeably and refer to an -SR s group.

[0055] The term "selenoalkyl" refers to a -SeR s group.

[0056] The term "sulfinyl" refers to a -S(O)-R s group.

[0057] The term "sulfonyl" refers to a -SO2-R s group.

[0058] The term "phosphino group" 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.

[0059] The term "silyl group" 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.

[0060] The term "germyl group" 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.

[0061] The term "boryl group" 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.

[0062] 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.

[0063] The term "alkyl" means and includes both straight-chain and branched-chain alkyl groups having alkyl carbon atoms bonded to the relevant structure. Preferred alkyl groups are those containing from one to fifteen carbon atoms, preferably from one to nine carbon atoms, and include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,3-dimethylpropyl, 1,1-dimethylpropyl, 2-ethylpropyl, 1,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, and the like. Additionally, the alkyl group may be further substituted.

[0064] The term "cycloalkyl" means and includes monocyclic, polycyclic, and spirocyclic alkyl groups having cycloalkyl carbon atoms bonded to the relevant structure. Preferred cycloalkyl groups are those containing 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, and the like. Additionally, the cycloalkyl group may be further substituted.

[0065] The terms "heteroalkyl" or "heterocycloalkyl" mean an alkyl or cycloalkyl group 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 group may be further substituted.

[0066] The term "alkenyl" means and includes both straight-chain and branched-chain alkene groups. An alkenyl group is essentially an alkyl group that includes at least one carbon-carbon double bond in the alkyl chain, where one of the carbon atoms is from the carbon-carbon double bond bonded to the relevant structure. A cycloalkenyl group is essentially a cycloalkyl group that includes at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" means an alkenyl group 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 alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing from two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be further substituted.

[0067] The term "alkynyl" means and includes both straight-chain and branched-chain alkyne groups. An alkynyl group is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain, where one of the carbon atoms is from the carbon-carbon triple bond bonded to the relevant structure. Preferred alkynyl groups are those containing from two to fifteen carbon atoms. Additionally, the alkynyl group may be further substituted.

[0068] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an aryl-substituted alkyl group having an alkyl carbon atom bonded to the relevant structure. Additionally, the aralkyl group may be further substituted.

[0069] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic 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. The heteroaromatic cyclic group may be used interchangeably with heteroaryl. 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 may be further substituted or fused.

[0070] The term "aryl" refers to and includes both monocyclic and polycyclic aromatic hydrocarbon groups. The polycycle may 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 may be further substituted or fused, such as but not limited to fluorene.

[0071] The term "heteroaryl" refers to 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 can have one to six heteroatoms. The polycyclic heterocyclic system can 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 can 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 can be further substituted or fused.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] In still other cases, the most preferred general substituents are selected from the group consisting of: deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0078] 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 at 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 substitution for ring atoms with fully saturated valences, such as the nitrogen atom in pyridine. The maximum possible number of substitutions in the ring structure will depend on the total number of available valences in the ring atoms.

[0079] As used herein, "a combination thereof" means that one or more members of an applicable list are combined to form a known or chemically stable arrangement that a person of ordinary skill in the art can envision from the applicable list. By way of example, an alkyl group and deuterium can be combined to form a partially or fully deuterated alkyl group; a halogen and an alkyl group can be combined to form a haloalkyl substituent; and a halogen, an alkyl group, and an aryl group can be combined to form a haloarylalkyl group. 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.

[0080] 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 a person of ordinary skill in the art, and all such analogs are intended to be encompassed by the terms as set forth herein.

[0081] 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 efficient routes for the deuteration of methylene hydrogens in benzylamines and the replacement of aromatic ring hydrogens with deuterium, respectively.

[0082] 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 without a valence fully filled by H or D in a chemical structure 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.

[0083] 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 a 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.

[0084] In some cases, a pair of substituents in a molecule may join or fuse 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 join or fuse 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).

[0085] B. Compounds of the Present Disclosure

[0086] In one aspect, the present disclosure provides a compound having the formula Ir(L A ) x (L B ) y (Lc) z wherein:

[0087] L A has a structure of Formula IA:

[0088] L B has a structure of Formula IB:

[0089] L C is a bidentate ligand;

[0090] x is 1 or 2; y is 1 or 2; z is 0 or 1; and x + y + z = 3;

[0091] The structure of Formula II is fused to at least one of moieties A, B, C, or D;

[0092] W 1 to W 8 each independently is C or N;

[0093] Each of moiety A, moiety B, moiety C, and moiety D is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5 - to 10 - membered carbocyclic or heterocyclic ring;

[0094] n is 1, 2, or 3;

[0095] The dashed line in Formula II represents a direct bond to two adjacent carbon atoms;

[0096] R A’ , R B’ , R C’ , R D’ and R E each independently represents mono - substitution to the maximum allowable substitution or no substitution;

[0097] Each R A’ , R B’ , R C’ , R D’ and R E 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, selenyl, and combinations thereof; and

[0098] Any two substituents may be fused or joined to form a ring.

[0099] In some embodiments, at least one of moiety A or moiety B is a polycyclic fused ring system comprising at least four rings fused together. In some such embodiments, Formula II may be fused to a polycyclic fused ring system comprising at least four rings fused together. In some such embodiments, at least one R A’ , R B’ , R C’ or R D’ is deuterium, an EWG group, silyl, or germyl. In some such embodiments, at least one R C’ or R D’is deuterium, an EWG group, a silyl group, or a germyl group. In some such embodiments, at least one R C’ or R D’ is deuterium. In some such embodiments, at least one R E is CD3.

[0100] In some embodiments, at least one of moiety A or moiety B is a polycyclic fused-ring system comprising at least three rings fused together, and R A’ , R B’ , R C’ , R D’ and R E independently comprises an electron-withdrawing group, a silyl group, or a germyl group. In some such embodiments, Formula II may be fused to a polycyclic fused-ring system comprising at least three rings fused together.

[0101] In some embodiments, at least one of moiety A or moiety B is carbazole, aza-carbazole, fluorene, or aza-fluorene.

[0102] In some embodiments, at least one of the following conditions is true:

[0103] (1) At least one of moiety A or moiety B is a polycyclic fused-ring system comprising at least four rings fused together;

[0104] (2) At least one of moiety A or moiety B is a polycyclic fused-ring system comprising at least three rings fused together, and R A’ , R B’ , R C’ , R D’ and R E independently comprises an electron-withdrawing group, a silyl group, or a germyl group;

[0105] (3) At least one of moiety A or moiety B is carbazole, aza-carbazole, fluorene, or aza-fluorene.

[0106] In some embodiments, the compound is not:

[0107]

[0108] In some embodiments, the compound has the formula Ir(L A ) x (L B ) y , which has the structure of Formula I: wherein x is 1 and y is 2, or x is 2 and y is 1; and the remaining variables are as defined previously.

[0109] In some embodiments, the formula Ir(LA ) x (L B ) y has the structure of Formula I. In some embodiments, Formula Ir(L A ) x (L B ) y consists essentially of the structure of Formula I.

[0110] In some embodiments of Formula I, at least one R A’ 、R B’ 、R C’ or R D’ is deuterium, an EWG group, a silyl group or a germyl group. In some such embodiments, at least one R C’ or R D’ is deuterium, an EWG group, a silyl group or a germyl group. In some such embodiments, at least one R C’ or R D’ is deuterium. In some such embodiments, at least one R E is CD3.

[0111] In some embodiments, at least one R A’ 、R B’ 、R C’ 、R D’ or R E is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R A’ is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R B’ is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R C’ is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R D’ is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R E is a substituent selected from the group consisting of the general substituents defined herein.

[0112] In some embodiments of Formula I, at least one R A’ 、R B’ 、R C’ 、R D’ or R E 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 RC’ is partially or fully deuterated. In some embodiments, at least one R D’ is partially or fully deuterated. In some embodiments, at least one R E is partially or fully deuterated.

[0113] In some embodiments, each of moiety A, moiety B, moiety C, and moiety D is independently a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic or polycyclic fused ring system is independently a 5- or 6-membered carbocyclic or heterocyclic ring.

[0114] In some embodiments, each of moiety A, moiety B, moiety C, and moiety D is independently 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.

[0115] In some embodiments, each R A’ , R B’ , R C’ , R D’ and R E is independently hydrogen or a substituent selected from the group consisting of preferred general substituents as defined herein. In some embodiments, each R A’ , R B’ , R C’ , R D’ and R E is independently hydrogen or a substituent selected from the group consisting of more preferred general substituents as defined herein. In some embodiments, each R A’ , R B’ , R C’ , R D’ and R E is independently hydrogen or a substituent selected from the group consisting of most preferred general substituents as defined herein.

[0116] In some embodiments, x is 1 and y is 2. In some embodiments, x is 2 and y is 1.

[0117] In some embodiments, W 1 is N and W 2 , W 5 and W 6 are each C.

[0118] In some embodiments, W 1 is the carbene C, W 5 is N and W 2 and W 6 are C.

[0119] In some embodiments, W 3 is N and W4 , W 7 and W 8 each of which is C.

[0120] In some embodiments, W 3 is a carbene C, W 7 is N and W 4 and W 8 are C.

[0121] In some embodiments, the structure of Formula II is fused to moiety A.

[0122] In some embodiments, moiety A is a polycyclic fused-ring system comprising at least four rings fused together. In some embodiments, moiety A is a polycyclic fused-ring system comprising at least five rings fused together. In some embodiments, the structure of Formula II is fused to the distal ring of the polycyclic fused-ring system of moiety A. In some embodiments, the structure of Formula II is fused to a ring other than the distal ring of the polycyclic fused-ring system of moiety A. As used herein, the "distal" ring refers to the ring in the polycyclic fused-ring system that is farthest from the Ir atom.

[0123] In some embodiments, moiety A is not a polycyclic fused-ring system comprising at least four rings fused together (i.e., moiety B is a monocyclic or polycyclic fused-ring system comprising at most three rings fused together).

[0124] In some embodiments, the structure of Formula II is fused to moiety B.

[0125] In some embodiments, moiety B is a polycyclic fused-ring system comprising at least four rings fused together. In some embodiments, moiety B is a polycyclic fused-ring system comprising at least five rings fused together. In some embodiments, the structure of Formula II is fused to the distal ring of the polycyclic fused-ring system of moiety B. In some embodiments, the structure of Formula II is fused to a ring other than the distal ring of the polycyclic fused-ring system of moiety B. As used herein, the "distal" ring refers to the ring in the polycyclic fused-ring system that is farthest from the Ir atom.

[0126] In some embodiments, moiety B is not a polycyclic fused-ring system comprising at least four rings fused together (i.e., moiety B is a monocyclic or polycyclic fused-ring system comprising at most three rings fused together).

[0127] In some embodiments, the structure of Formula II is fused to moiety C.

[0128] In some embodiments, moiety C is a monocyclic ring. In some embodiments, moiety C is pyridine. In some embodiments, when moiety C is pyridine and Formula II is fused to pyridine, then at least one R C or one R Dis deuterium, an EWG group, a silyl group, or a germyl group. In some such embodiments, at least one R C or one R D is deuterium. In some embodiments, when moiety C is pyridine and Formula II is fused to pyridine and moiety D is a monocyclic benzene ring, then at least one R E is an EWG group, a silyl group, a germyl group, or CD3. In some such embodiments, at least one R E is CD3. In some embodiments, moiety C is a polycyclic fused ring system. In some such embodiments, Formula II is fused to the polycyclic fused ring system.

[0129] In some embodiments, the structure of Formula II is fused to moiety D.

[0130] In some embodiments, moiety D is monocyclic. In some embodiments, moiety D is benzene. In some embodiments, when moiety D is benzene and Formula II is fused to benzene and moiety C is a monocyclic pyridine ring, then at least one R C or one R D is deuterium, an EWG group, a silyl group, or a germyl group. In some such embodiments, at least one R C or one R D is deuterium. In some embodiments, when moiety D is benzene and Formula II is fused to benzene, then at least one R E is an EWG group, a silyl group, a germyl group, or CD3. In some such embodiments, at least one R E is CD3.

[0131] In some embodiments, moiety D is a polycyclic fused ring system. In some such embodiments, Formula II is fused to the polycyclic fused ring system.

[0132] In some embodiments, at least one structure of Formula II is fused to moiety A or moiety B. In some embodiments, at least one structure of Formula II is fused to moiety A. In some embodiments, at least one structure of Formula II is fused to moiety B.

[0133] In some embodiments, at least one structure of Formula II is fused to moiety C or moiety D. In some embodiments, at least one structure of Formula II is fused to moiety C. In some embodiments, at least one structure of Formula II is fused to moiety D.

[0134] In some embodiments, at least one structure of Formula II is fused to moiety A or moiety B, and at least one structure of Formula II is fused to moiety C or moiety D.

[0135] In some embodiments, each of moiety A, moiety B, moiety C, and moiety D is independently selected from the group consisting of moieties composed of two structures from a list of cyclic moieties or a list of fused cyclic moieties; wherein the list of cyclic moieties is defined as benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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.

[0136] In some embodiments, moiety A is a monocyclic ring. In some embodiments, moiety A is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, moiety A is pyridine or imidazole.

[0137] In some embodiments, moiety A is a polycyclic fused ring system. In some embodiments, moiety A is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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, moiety A is quinoline, isoquinoline, or benzimidazole.

[0138] In some embodiments, moiety A contains at least four fused rings. In some embodiments, moiety A contains at least five fused rings.

[0139] In some embodiments, containing W 1The ring of is part of part A1, and the part 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. In some embodiments, containing W 1 The ring of is pyridine or imidazole. In some embodiments, containing W 1 The ring of is pyridine. In some embodiments, containing W 1 The ring of is imidazole.

[0140] In some embodiments, part A1 is cyclized by part A2 whose ring is selected from the list of cyclic parts defined herein. In some embodiments, part A2 is benzene, naphthalene, benzofuran, or benzothiophene. In some embodiments, part A2 is benzene. In some embodiments, part A2 is naphthalene.

[0141] In some embodiments, part A1 is aza-dibenzofuran and A2 is benzene or naphthalene.

[0142] In some embodiments, part B is a monocyclic ring. In some embodiments, part B is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, part B is pyridine or imidazole.

[0143] In some embodiments, part B is a polycyclic fused ring system. In some embodiments, part B is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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, part B is quinoline, isoquinoline, or benzimidazole.

[0144] In some embodiments, part B contains at least four rings fused together. In some embodiments, part B contains at least five rings fused together.

[0145] In some embodiments, containing W 2The ring of is part of part B1, and the part 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. In some embodiments, containing W 2 The ring of is benzene.

[0146] In some embodiments, part B1 is cyclized by part B2, where part B2 is selected from the group consisting of the list of cyclic moieties defined herein. In some embodiments, part B2 is benzene, naphthalene, benzofuran, or benzothiophene. In some embodiments, part B is benzene. In some embodiments, part B is naphthalene.

[0147] In some embodiments, part B1 is dibenzofuran and B2 is benzene or naphthalene.

[0148] In some embodiments, part C is a monocyclic ring. In some embodiments, part C 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, part C is pyridine or imidazole.

[0149] In some embodiments, part C is a polycyclic fused ring system. In some embodiments, part C is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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, part C is naphthalene or benzimidazole.

[0150] In some embodiments, part D is a monocyclic ring. In some embodiments, part D 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, part D is benzene.

[0151] In some embodiments, moiety D is a polycyclic fused-ring system. In some embodiments, moiety D is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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, moiety D is naphthalene.

[0152] In some embodiments, each of moiety A, moiety B, moiety C, and moiety D can independently be a polycyclic fused-ring structure. In some embodiments, each of moiety A, moiety B, moiety C, and moiety D can independently 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, each of moiety A, moiety B, moiety C, and moiety D can independently be selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene, and their aza-variants. In some such embodiments, each of moiety A, moiety B, moiety C, and moiety D can independently 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), while containing a substituent at the 7-position (meta to O, S, or Se).

[0153] In some embodiments, each of moiety A, moiety B, moiety C, and moiety D can independently 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.

[0154] In some embodiments, each of moiety A, moiety B, moiety C, and moiety D can independently be a polycyclic fused-ring structure containing at least five fused rings. In some embodiments, the polycyclic fused-ring structure contains four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments containing two 5-membered rings, the 5-membered rings are fused together. In some embodiments containing 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, a second 6-membered ring is fused to the 5-membered ring, a third 6-membered ring is fused to the second 6-membered ring, and a fourth 6-membered ring is fused to the third 6-membered ring.

[0155] In some embodiments, each of moiety A, moiety B, moiety C, and moiety D can independently be the aza form of the polycyclic fused-ring described above. In some such embodiments, each of moiety A, moiety B, moiety C, and moiety D can independently contain exactly one aza N atom. In some such embodiments, each of moiety A, moiety B, moiety C, and moiety D 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.

[0156] In some embodiments, n is 1. In some embodiments, n is 2. In some embodiments, n is 3.

[0157] In some embodiments, the compound contains an electron-withdrawing group. In some embodiments, 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.

[0158] In some embodiments, the formula Ir(L A ) x (L B ) y contains an electron-withdrawing group selected from the group consisting of the following EWG1 list: 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(Rk2 ) 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,

[0159] wherein each R k1 represents mono-substitution to the maximum allowable substitution or no substitution; and

[0160] wherein R k1 , R k2 , R k3 , R e and R f each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein.

[0161] In some embodiments, the formula Ir(L A ) x (L B ) y comprises an electron-withdrawing group selected from the group consisting of the structures of the following EWG2 list:

[0162]

[0163]

[0164] In some embodiments, the formula Ir(L A ) x (L B ) y comprises an electron-withdrawing group selected from the group consisting of the structures of the following EWG3 list:

[0165]

[0166] In some embodiments, the formula Ir(L A ) x (L B ) y comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG4 list:

[0167] In some embodiments, the formula Ir(L A ) x (L B ) y comprises an electron-withdrawing group, and the electron-withdrawing group 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 , a substituted or unsubstituted dibenzoborolene, a 1-substituted carbazole, a 1,9-substituted carbazole, a substituted or unsubstituted carbazole, a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted pyridazine, a substituted or unsubstituted triazine, a substituted or unsubstituted oxazole, a substituted or unsubstituted benzoxazole, a substituted or unsubstituted thiazole, a substituted or unsubstituted benzothiazole, a substituted or unsubstituted imidazole, a substituted or unsubstituted benzimidazole, a ketone, a carboxylic acid, an ester, a nitrile, an isonitrile, a sulfinyl group, a sulfonyl group, a partially and fully fluorinated aryl group, a partially and fully fluorinated heteroaryl group, an aryl group containing a cyano group, a heteroaryl group containing a cyano group, an isocyanate,

[0168] wherein the variables are the same as those defined previously.

[0169] In some embodiments, the ligand LA comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, ligand L A comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, ligand L A comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, ligand L A comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, ligand L A comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0170] In some embodiments, ligand L B comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, ligand L B comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, ligand L B comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, ligand L B comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, ligand L B comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0171] 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 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.

[0172] 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.

[0173] In some embodiments, at least one R C’ is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C’ is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C’ is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0174] In some embodiments, at least one R D’ is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R D’ is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R D’ is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0175] In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0176] In some embodiments, at least one R that is not part of Formula IIA’ Not hydrogen.

[0177] In some embodiments, at least one R that is not part of Formula II A’ contains at least one C atom. In some embodiments, at least one R that is not part of Formula II A’ contains at least three C atoms. In some embodiments, at least one R that is not part of Formula II A’ contains at least four C atoms.

[0178] In some embodiments, at least one R that is not part of Formula II A’ contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0179] In some embodiments, at least one R that is not part of Formula II B’ is not hydrogen.

[0180] In some embodiments, at least one R that is not part of Formula II B’ contains at least one C atom. In some embodiments, at least one R that is not part of Formula II B’ contains at least three C atoms. In some embodiments, at least one R that is not part of Formula II B’ contains at least four C atoms.

[0181] In some embodiments, at least one R that is not part of Formula II B’ contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0182] In some embodiments, at least one R that is not part of Formula II C’ is not hydrogen.

[0183] In some embodiments, at least one R that is not part of Formula II C’ contains at least one C atom. In some embodiments, at least one R that is not part of Formula II C’ contains at least three C atoms. In some embodiments, at least one R that is not part of Formula II C’ contains at least four C atoms.

[0184] In some embodiments, at least one R that is not part of Formula II C’ contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0185] In some embodiments, at least one R that is not part of Formula II D’ is not hydrogen.

[0186] In some embodiments, at least one R that is not part of Formula II D’ contains at least one C atom. In some embodiments, at least one R that is not part of Formula II D’ contains at least three C atoms. In some embodiments, at least one R that is not part of Formula II D’ contains at least four C atoms.

[0187] In some embodiments, at least one R that is not part of Formula II D’ contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0188] In some embodiments, at least one R E is not hydrogen.

[0189] In some embodiments, at least one R E contains at least one C atom. In some embodiments, at least two Rs E each independently contain at least one C atom. In some embodiments, at least three Rs E each independently contain at least one C atom. In some embodiments, at least four Rs E each independently contain at least one C atom.

[0190] In some embodiments, at least one R E contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, wherein at least two Rs E each independently contain substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0191] In some embodiments, any Rs on the same carbon E are the same. In some such embodiments, each R on the same carbon E is methyl. In some such embodiments, each R on the same carbon E is ethyl.

[0192] In some embodiments, two Rs on adjacent carbons E are joined or fused to form a ring. In some embodiments, two Rs on the same carbon E are joined or fused to form a spiro ring.

[0193] In some embodiments, the structure of Formula II is selected from the structures of List 1A below:

[0194]

[0195] wherein ring G or ring E is a 5- to 10-membered carbocyclic or heterocyclic ring;

[0196] R G represents mono-substitution to the maximum allowable substitution or no substitution;

[0197] each R G 、R E 、R E1 、R E2 、R E3 、R E4 、R E5 and R E6 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, selenyl, and combinations thereof; and any two substituents may be joined or fused to form a ring.

[0198] In some embodiments where the structure is from Listing 1A, at least one R G 、R E 、R E1 、R E2 、R E3 、R E4 、R E5 and R E6 is a substituent selected from the group of general substituents as defined herein. In some embodiments, at least one R G is a substituent selected from the group of general substituents as defined herein. In some embodiments, at least one R E is a substituent selected from the group of general substituents as defined herein. In some embodiments, at least one R E1 is a substituent selected from the group of general substituents as defined herein. In some embodiments, at least one R E2 is a substituent selected from the group of general substituents as defined herein. In some embodiments, at least one R E3 is a substituent selected from the group of general substituents as defined herein. In some embodiments, at least one R E4 is a substituent selected from the group of general substituents as defined herein. In some embodiments, at least one R E5 is a substituent selected from the group of general substituents as defined herein. In some embodiments, at least one R E6is a substituent selected from the group consisting of general substituents as defined herein. In some embodiments of the structure from Listing 1A, at least one R G , R E , R E1 , R E2 , R E3 , R E4 , R E5 , and R E6 contains at least two carbon atoms.

[0199] In some embodiments of the structure from Listing 1A, when R E1 and R E2 are connected to the same carbon atom, they can join to form a spiro structure.

[0200] In some embodiments of the structure from Listing 1A, when R E3 and R E4 are connected to the same carbon atom, they can join to form a spiro structure.

[0201] In some embodiments of the structure from Listing 1A, when R E5 and R E6 are connected to the same carbon atom, they can join to form a spiro structure.

[0202] In some of the above embodiments, the spiro ring can be a 5- to 10-membered carbocyclic or heterocyclic ring.

[0203] In some embodiments of the structure from Listing 1A, at least one of R E1 , R E2 , R E3 , R E4 , R E5 , and R E6 is an electron-withdrawing group.

[0204] In some embodiments, the structure of Formula II is selected from the structures of Listing 1 below:

[0205]

[0206] In some embodiments, the ligand L A is selected from the group consisting of the structures of Listing 2 below:

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215] Wherein:

[0216] Z 7 to Z 16 each independently is C or N;

[0217] Y is selected from the group consisting of: BR e , NR e , PR e , O, S, Se, C═O, C═S, C═Se, S═O, SO2, C═CR e R f , C═NR e , CR e R f , P(O)R e , SiR e R f and GeR e R f ;

[0218] Y1 is selected from the group consisting of: B, N, P, CR e , SiR e and GeR e ;

[0219] R AA and R BB each independently represents mono-substitution to the maximum allowable substitution or no substitution;

[0220] Each R AA , R BB , R N , R e and R f is independently hydrogen or a substituent selected from the group of general substituents defined herein; and

[0221] any two substituents may be joined or fused to form a ring.

[0222] In some embodiments where the ligand L A is selected from List 2, when L B the ligand does not contain the structure of Formula II, at least one pair of R AA or R BBJoin to form a structure of Formula II.

[0223] In ligand L A In some embodiments selected from List 2, at least one R AA or R BB is a substituent selected from the group consisting of general substituents defined herein. In some embodiments, at least one R AA is a substituent selected from the group consisting of general substituents defined herein. In some embodiments, at least one R BB is a substituent selected from the group consisting of general substituents defined herein.

[0224] In ligand L A In some embodiments selected from List 2, at least one R AA 、R BB 、R N 、R e and R f is partially or fully deuterated. In some embodiments, at least one R AA is partially or fully deuterated. In some embodiments, at least one R BB is partially or fully deuterated. In some embodiments, at least one R N is partially or fully deuterated. In some embodiments, at least one R e or R f is partially or fully deuterated.

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

[0227] In some embodiments of ligand L A 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.

[0228] In some embodiments of ligand L A 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.

[0229] In some embodiments, ligand L A is selected from the group consisting of the structures of List 2a below:

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240] Wherein:

[0241] X1 to X 19 are each independently C or N;

[0242] Y1, Y A , Y B and Y C 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 ;

[0243] Each R A1 , R B1 , R B2 and R B3 independently represents mono-substituted to the maximum possible number of substitutions or unsubstituted;

[0244] Each R A1 , R B1 , R B2 , R B3 , R e and R f independently is hydrogen or a substituent selected from the group of general substituents defined herein; and

[0245] Any two substituents may be joined or fused to form a ring.

[0246] In ligand L A In some embodiments selected from List 2a, when L B the ligand does not contain the structure of Formula II, at least one pair of R A1 、R B1 、R B2 or R B3 are joined to form the structure of Formula II.

[0247] In some embodiments, the ligand L A is selected from the group consisting of the structures of List 3 below:

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262] Wherein:

[0263] Each of X and Y is independently selected from the group consisting of: BR e 、NR e 、PR e 、O、S、Se、C=O、C=S、C=Se、S=O、SO2、C=CR e R f 、C=NR e 、CR eR f 、P(O)R e 、SiR e R f and GeR e R f ;

[0264] R AA , R BB and R C Each of the above independently represents mono-substitution to the maximum permissible substitution or no substitution;

[0265] Each R AA , R BB , R C , R e , R f and R N is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0266] Any two substituents may be joined or fused to form a ring.

[0267] In ligand L A In some embodiments selected from Listing 3, when L B When the ligand does not contain the structure of formula II, at least one pair of R AA , R BB or R C Joining occurs to form the structure of Formula II.

[0268] In ligand L A In some embodiments selected from Listing 3, at least one R AA , R BB or R C is a substituent selected from the group consisting of general substituents defined herein. In some embodiments, at least one R AA is a substituent selected from the group consisting of general substituents defined herein. In some embodiments, at least one R BB is a substituent selected from the group consisting of general substituents defined herein. In some embodiments, at least one R C is a substituent selected from the group consisting of general substituents defined herein.

[0269] In ligand L A In some embodiments selected from Listing 3, R e , R f , R AA , R BB , R C or R N At least one of R AAis partially or fully deuterated. In some embodiments, at least one R BB is partially or fully deuterated. In some embodiments, at least one R C is partially or fully deuterated. In some embodiments, at least one R N is partially or fully deuterated. In some embodiments, at least one R e or R f is partially or fully deuterated.

[0270] In some embodiments where the ligand L A is selected from List 3, at least one R AA is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AA is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AA is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AA is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AA is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0271] In some embodiments where the ligand L A is selected from List 3, at least one R BB is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R BB is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R BB is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R BB is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R BB is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0272] In some embodiments where the ligand L A is selected from List 3, at least one R C is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R Cis or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0273] In ligand L A In some embodiments where it is selected from List 3, 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.

[0274] In ligand L A In some embodiments where it is selected from List 3, 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.

[0275] In some embodiments, ligand L A is selected from L A’w (G A )(R H )(R I )(R J )(R K ), where w is an integer from 1 to 72, and R H, R I , R J and R K each independently selected from the group consisting of V1 to V148; G A is selected from G1 to G57, and L A’1 (G1)(V1)(V1)(V1)(V1) to L A’72 (G57)(V148)(V148)(V148)(V148) are each defined in the following List 3a:

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283] wherein each of V1 to V148 is defined as follows:

[0284]

[0285] and

[0286] wherein each of G1 to G57 is defined as follows:

[0287]

[0288] In some embodiments, the ligand L A is selected from L A*w’ (R H )(R I )(R J )(R K ), where w’ is an integer from 1 to 28, and R H , R I , R J and R KEach of which is independently selected from the group consisting of V1 to V148; and L A*1 (V1)(V1)(V1)(V1) to L A*28 (V148)(V148)(V148)(V148) each of which is defined below (Listing 3b):

[0289]

[0290]

[0291]

[0292] In some embodiments, the ligand L A is selected from L Ai , where i is an integer from 1 to 420, and each of L A1 to L A420 is defined in Listing 4 below:

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315] In some embodiments, L B is selected from the group consisting of the structures of List 5 below:

[0316]

[0317]

[0318]

[0319] wherein:

[0320] T is selected from the group consisting of B, Al, Ga, and In;

[0321] 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 ;

[0322] Y 1 to Y 13 each independently is selected from the group consisting of C and N;

[0323] 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 Rf and GeR e R f ;

[0324] R e and R f may be fused or joined to form a ring;

[0325] Each R a 、R b 、R c and R d independently represents mono-substituted to the maximum allowable number of substitutions or unsubstituted;

[0326] 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 consisting of the general substituents defined herein; and

[0327] R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c and R d any two substituents among them may be fused or joined to form a ring or form a polydentate ligand.

[0328] In some embodiments where L B is selected from List 5 defined herein, when L A does not contain the structure of Formula II, at least two adjacent R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c and R d are joined or fused to form the structure of Formula II. In some embodiments where L B is selected from List 5 defined herein, two adjacent R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c or R dJoin or fuse to form a structure of Formula II, even if L A also contains a structure of Formula II. In some embodiments, L B is selected from the group consisting of the structures of List 6 below:

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335] Wherein:

[0336] 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 respective rings;

[0337] 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

[0338] R a ’, R b ’, R c ’, R d ’ and R e ’ can be fused or joined to form a ring or form a polydentate ligand.

[0339] In some embodiments where L B is selected from List 6 defined herein, when L A does not contain a structure of Formula II, at least two adjacent R a ’, R b ’, R c ’, R d ’ or R e ’ are joined or fused to form a structure of Formula II. In L BIn some embodiments selected from List 6 as defined herein, two adjacent R a ’, R b ’, R c ’, R d ’ or R e ’ are joined or fused to form a structure of Formula II, even if L A also contains a structure of Formula II.

[0340] In some embodiments, L B contains the following structure: wherein the variables are the same as those defined previously. In some embodiments, each of Y 1 to Y 4 is independently carbon. In some embodiments, at least one of Y 1 to Y 4 is N. In some embodiments, exactly one of Y 1 to Y 4 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 are joined or fused to form a ring.

[0341] In some embodiments, L A may be selected from L Ai, where i is an integer from 1 to 420; and L B can be selected from L Bk , where k is an integer from 1 to 530, and where:

[0342] When the compound has the formula Ir(L Ai )(L Bk )2, the compound is selected from the group consisting of Ir(L A1 )(L B1 )2 to Ir(L A420 )(L B530 )2;

[0343] 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 A420 )2(L B530 );

[0344] where each L Bk has the structure defined in List 7 below:

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359] In some embodiments, L B is selected from L B’g , where g is an integer from 1 to 57, and each L B’g is defined in Listing 6a below:

[0360]

[0361]

[0362] In some embodiments, L A is optionally selected from L A’w (G A )(R H )(R I )(R J )(R K ), where w is an integer from 1 to 72, and L B is optionally selected from L Bk , where k is an integer from 1 to 530, and L B is optionally selected from L Bk , where:

[0363] When the compound has the formula Ir(L A’w (G A )(R H )(R I )(R J )(R K ))(L Bk )2, the compound is selected from the group consisting of Ir(L A’1 (G1)(V1)(V1)(V1)(V1))(L B1 )2 to Ir(L A’72 (G57)(V148)(V148)(V148)(V148))(L B530 )2;

[0364] When the compound has the formula Ir(L A’w (G A )(R H )(R I )(R J )(R K ))2(L Bk ), the compound is selected from the group consisting of Ir(L A’1 (G1)(V1)(V1)(V1)(V1))2(L B1 ) to Ir(L A’72 (G57)(V148)(V148)(V148)(V148))2(L B530 ).

[0365] In some embodiments, L A is optionally selected from L A*w’ (R H )(R I )(R J )(R K ), where w’ is an integer from 1 to 28; and L B is optionally selected from L B’g , where g is an integer from 1 to 57, wherein:

[0366] When the compound has the formula Ir(L A*w’ (R H )(R I )(R J )(R K ))(L B’g )2, the compound is selected from the group consisting of Ir(L A’1 (V1)(V1)(V1)(V1))(L B’1 )2 to Ir(L A’28 (V148)(V148)(V148)(V148))(L B’57 )2;

[0367] When the compound has the formula Ir(L A*w’ (R H )(R I )(R J )(R K ))2(L B’g ), the compound is selected from the group consisting of Ir(L A’1 (V1)(V1)(V1)(V1))2(L B’1 ) to Ir(L A’28 G57)(V148)(V148)(V148)(V148))2(L B’57 );

[0368] In some embodiments, L A is optionally selected from L A’w (G A )(R H )(R I )(R J )(R K ), where w is an integer from 1 to 72; and L B is optionally selected from L B’g , where g is an integer from 1 to 57, wherein:

[0369] When the compound has the formula Ir(L A’w (G A )(R H )(RI )(R J )(R K ))(L B’g )2, the compound is selected from the group consisting of Ir(L A’1 (G1)(V1)(V1)(V1)(V1))(L B1 )2 to Ir(L A’72 (G57)(V148)(V148)(V148)(V148))(L B530 )2;

[0370] When the compound has the formula Ir(L A’w (G A )(R H )(R I )(R J )(R K ))2(L B’g )), the compound is selected from the group consisting of Ir(L A’1 (G1)(V1)(V1)(V1)(V1))2(L B1 ) to Ir(L A’72 (G57)(V148)(V148)(V148)(V148))2(L B’57 ));

[0371] In some embodiments, the compound is selected from the group consisting of the structures of List 8 below:

[0372]

[0373]

[0374]

[0375] In another aspect, an Ir complex is provided, which comprises a ligand L having a structure comprising Formula III: The ligand L A” ), and Formula III comprises the structure of Formula II, which is fused to Ring H or Ring G.

[0376] In Formula III:

[0377] Moiety F 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;

[0378] X 1 to X 10 each of which is independently C or N;

[0379] YA 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’;

[0380] n is 1, 2 or 3;

[0381] The dashed line in Formula II represents a direct bond to two adjacent carbon atoms;

[0382] R E 、R F 、R G and R H each independently represents mono-substitution to the maximum allowable substitution or no substitution;

[0383] wherein each R, R’, R E 、R F 、R G and R H is independently hydrogen or a substituent selected from the group of general substituents defined herein;

[0384] wherein any two substituents may be joined or fused to form a ring.

[0385] In some embodiments of Formula III, if Ring F is pyridine, then each of the following is true:

[0386] (1) Any two R substituents bonded to the same carbon atom are the same;

[0387] (2) R E is not fluorine;

[0388] (3) If two R E are bonded to the same carbon, then they do not join to form a spiro center; and

[0389] (4) Formula II is not fused to X 6 and X 7 。

[0390] In some embodiments, the ligand L A” has the structure of Formula III. In some embodiments, the ligand L A” has a structure consisting essentially of Formula III.

[0391] Although described in separate aspects, it should be understood that the teachings applicable to L A are also applicable to L A” 。Similarly, in some embodiments, L A and L A” may be interchangeable (e.g., L A”can be used in the case of L of the compound of formula I B while L A can be used in the case of L B or L C of the compound of formula III).

[0392] In some embodiments of formula III, at least one R E 、R F 、R G or R H is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R E is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R F is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R G is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R H is a substituent selected from the group consisting of the general substituents defined herein.

[0393] In some embodiments of formula III, at least one R, R’, R E 、R F 、R G and R H are partially or fully deuterated. In some embodiments, at least one R E is partially or fully deuterated. In some embodiments, at least one R F is partially or fully deuterated. In some embodiments, at least one R G is partially or fully deuterated. In some embodiments, at least one R H is partially or fully deuterated. In some embodiments, at least one R or R’ is partially or fully deuterated.

[0394] In some embodiments of formula III, part F 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.

[0395] In some embodiments of formula III, part F 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.

[0396] In some embodiments of formula III, each R, R’, R E 、R F 、R G and R HIndependently is hydrogen or a substituent 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.

[0397] In some embodiments of Formula III, X 10 is N and X 9 is C.

[0398] In some embodiments of Formula III, X 10 is a carbene carbon and X 9 is N.

[0399] In some embodiments of Formula III, each of X 1 to X 8 is carbon. In some embodiments of Formula III, at least one of X 1 to X 8 is N. In some embodiments of Formula III, exactly one of X 1 to X 8 is N.

[0400] In some embodiments of Formula III, each of X 1 to X 4 is C. In some embodiments of Formula III, at least one of X 1 to X 4 is N. In some embodiments of Formula III, exactly one of X 1 to X 4 is N.

[0401] In some embodiments of Formula III, each of X 5 to X 8 is C. In some embodiments of Formula III, at least one of X 5 to X 8 is N. In some embodiments of Formula III, exactly one of X 5 to X 8 is N.

[0402] In some embodiments of Formula III, Y A is selected from the group consisting of O, S and Se. In some embodiments, Y A is O. In some embodiments, Y A is selected from the group consisting of BR, NR and PR. In some embodiments, Y A is BR. In some embodiments, Y A is NR. In some embodiments, Y A is PR. In some embodiments, YA 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 A is selected from the group consisting of: BRR′, CRR′, SiRR′, and GeRR′. In some embodiments, Y A is CR.

[0403] In some embodiments, the ring containing Y A is fused to ring G at X 3 and X 4 . In some embodiments, the ring containing Y A is fused to ring G at X 2 and X 3 . In some embodiments, the ring containing Y A is fused to ring G at X 1 and X 2 .

[0404] In some embodiments, the structure of formula II is fused to ring G. In some embodiments, the structure of formula II is fused to ring G at X 1 and X 2 . In some embodiments, the structure of formula II is fused to ring G at X 3 and X 4 .

[0405] In some embodiments, part F is selected from the group consisting of the list of cyclic moieties defined herein.

[0406] In some embodiments, part F is a single ring. In some embodiments, part F is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, part F is pyridine or imidazole.

[0407] In some embodiments, part F is a polycyclic fused-ring system. In some embodiments, part F is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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, part F is quinoline, isoquinoline, or benzimidazole.

[0408] In some embodiments, part F can be a polycyclic fused-ring structure. In some embodiments, part F can be a polycyclic fused-ring structure containing 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, part F can be selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and their aza-variants. In some such embodiments, part F 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).

[0409] In some embodiments, part F can be a polycyclic fused-ring structure containing at least four fused rings. In some embodiments, the polycyclic fused-ring structure contains 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.

[0410] In some embodiments, part F may be a polycyclic fused-ring structure containing at least five fused rings. In some embodiments, the polycyclic fused-ring structure contains four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments containing two 5-membered rings, the 5-membered rings are fused together. In some embodiments containing 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, a second 6-membered ring is fused to the 5-membered ring, a third 6-membered ring is fused to the second 6-membered ring, and a fourth 6-membered ring is fused to the third 6-membered ring.

[0411] In some embodiments, part F may be the aza form of the polycyclic fused-ring described above. In some such embodiments, part F may contain exactly one heteroatom. In some such embodiments, part F may contain exactly two hetero N atoms, which may be in one ring or in two different rings. In some such embodiments, the ring having the hetero N atom is separated from the Ir atom by at least two other rings. In some such embodiments, the ring having the hetero 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 hetero N atom is substituted.

[0412] In some embodiments, n is 1. In some embodiments, n is 2. In some embodiments, n is 3.

[0413] In some embodiments, the structure of formula II is fused to ring H at X 5 and X 6 . In some embodiments, the structure of formula II is fused to ring H at X 6 and X 7 . In some embodiments, the structure of formula II is fused to ring H at X 7 and X 8 .

[0414] In some embodiments, formula III contains an electron-withdrawing group selected from the group consisting of the list of EWG1 defined herein. In some embodiments, formula III contains an electron-withdrawing group from the list of EWG2 defined herein. In some embodiments, formula III contains an electron-withdrawing group from the list of EWG3 defined herein. In some embodiments, formula III contains an electron-withdrawing group from the list of EWG4 defined herein. In some embodiments, formula III contains an electron-withdrawing group from the list of Pi-EWG defined herein.

[0415] In some embodiments, ligand L is included A”The compound contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, the compound contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, the compound contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, the compound contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, the compound contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0416] In some embodiments, at least one R E is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R E is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R E is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R E is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R E is or contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0417] In some embodiments, at least one R F is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R F is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R F is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R F is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R F is or contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0418] In some embodiments, at least one R G is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R G is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R G is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R G is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one RG is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0419] In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0420] 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.

[0421] In some embodiments, at least one R F is not hydrogen. In some embodiments, at least one R F comprises at least one C atom. In some embodiments, at least one R F comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0422] In some embodiments, at least one R G is not hydrogen. In some embodiments, at least one R G comprises at least one C atom. In some embodiments, at least one R G comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, two R G are joined or fused to form a ring.

[0423] In some embodiments, at least one R H is not hydrogen. In some embodiments, at least one R HContains at least one C atom. In some embodiments, at least one R H Contains substituents selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, two Rs H Are joined or fused to form a ring other than the structure of Formula II.

[0424] In some embodiments, at least one R E Is not hydrogen. In some embodiments, at least one R E Contains at least one C atom. In some embodiments, at least two Rs E Each independently contains at least one C atom. In some embodiments, at least three Rs E Each independently contains at least one C atom. In some embodiments, at least four Rs E Each independently contains at least one C atom.

[0425] In some embodiments, at least one R E Contains substituents selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, at least two Rs E Independently contain substituents selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0426] In some embodiments, any Rs on the same carbon E Are the same. In some embodiments, any Rs on the same carbon E Are methyl. In some embodiments, any Rs on the same carbon E Are ethyl.

[0427] In some embodiments, two Rs on adjacent carbons E Are joined or fused to form a ring.

[0428] In some embodiments, two Rs on the same carbon E Are not H. In some embodiments, two Rs on the same carbon E Are joined or fused to form a ring.

[0429] In some embodiments of Formula I or Formula III, the structure of Formula II may be selected from the group consisting of the structures of List 1 as defined herein.

[0430] In some embodiments of Formula I or Formula III, the structure of Formula II may be selected from the group consisting of the structures of List 1A as defined herein.

[0431] In some embodiments, the ligand L A” Is selected from the group consisting of the structures of List 9 as follows:

[0432]

[0433]

[0434] Wherein:

[0435] X 11 to X 14 each independently is C or N;

[0436] Y is selected from the group consisting of: BR e , NR e , PR e , O, S, Se, C═O, C═S, C═Se, S═O, SO2, C═CR e R f , C═NR e , CR e R f , P(O)R e , SiR e R f and GeR e R f ;

[0437] Y1 is selected from the group consisting of: B, N, P, CR e , SiR e and GeR e ;

[0438] Each R N , R e and R f is independently hydrogen or a substituent selected from the group of general substituents defined herein; and

[0439] any two substituents may be fused or joined to form a ring.

[0440] In some embodiments of ligand L A” selected from List 9, at least one R F , R G or R H is a substituent selected from the group of general substituents defined herein. In some embodiments, at least one R F is a substituent selected from the group of general substituents defined herein. In some embodiments, at least one R G is a substituent selected from the group of general substituents defined herein. In some embodiments, at least one R H is a substituent selected from the group of general substituents defined herein.

[0441] In ligand L A”In some embodiments selected from Listing 9, at least one R F , R G , R H or R N is partially or fully deuterated. In some embodiments, at least one R F is partially or fully deuterated. In some embodiments, at least one R G is partially or fully deuterated. In some embodiments, at least one R H is partially or fully deuterated. In some embodiments, at least one R N is partially or fully deuterated.

[0442] In ligand L A” In some embodiments selected from Listing 9, at least one R F is or contains an electron-withdrawing group from the EWG1 listing as defined herein. In some embodiments, at least one R F is or contains an electron-withdrawing group from the EWG2 listing as defined herein. In some embodiments, at least one R F is or contains an electron-withdrawing group from the EWG3 listing as defined herein. In some embodiments, at least one R F is or contains an electron-withdrawing group from the EWG4 listing as defined herein. In some embodiments, at least one R F is or contains an electron-withdrawing group from the Pi-EWG listing as defined herein.

[0443] In ligand L A” In some embodiments selected from Listing 9, at least one R G is or contains an electron-withdrawing group from the EWG1 listing as defined herein. In some embodiments, at least one R G is or contains an electron-withdrawing group from the EWG2 listing as defined herein. In some embodiments, at least one R G is or contains an electron-withdrawing group from the EWG3 listing as defined herein. In some embodiments, at least one R G is or contains an electron-withdrawing group from the EWG4 listing as defined herein. In some embodiments, at least one R G is or contains an electron-withdrawing group from the Pi-EWG listing as defined herein.

[0444] In ligand L A” In some embodiments selected from Listing 9, at least one R H is or contains an electron-withdrawing group from the EWG1 listing as defined herein. In some embodiments, at least one R His or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0445] In ligand L A” In some embodiments where it is selected from List 9, 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.

[0446] In some embodiments, ligand L A” is selected from the group consisting of the structures of List 10 below:

[0447]

[0448]

[0449]

[0450]

[0451]

[0452]

[0453] Wherein:

[0454] Y A and Y B each is selected from the group consisting of: BR e 、NR e 、PR e 、O、S、Se、C=O、

[0455] C═S, C═Se, S═O, SO2, C═CR e R f , C═NR e , CR e R f , P(O)R e , SiR e R f and GeR e R f ;

[0456] R e and R f may be fused or joined to form a ring;

[0457] R F , R G and R H each independently represents mono-substitution to the maximum allowable substitution or no substitution;

[0458] R N , R F , R G and R H each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and

[0459] any two substituents may optionally be fused or joined to form a ring.

[0460] In some embodiments of ligand L A” selected from List 10, at least one R F , R G or R H is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R F is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R G is a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R H is a substituent selected from the group consisting of the general substituents defined herein.

[0461] In some embodiments of ligand L A” selected from List 10, at least one R F , R G , R H or R N is partially or fully deuterated. In some embodiments, at least one R F is partially or fully deuterated. In some embodiments, at least one R Gis partially or fully deuterated. In some embodiments, at least one R H is partially or fully deuterated. In some embodiments, at least one R N is partially or fully deuterated.

[0462] In ligand L A” In some embodiments where it is selected from List 10, at least one R F is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R F is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R F is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R F is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R F is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0463] In ligand L A” In some embodiments where it is selected from List 10, at least one R G is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R G is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R G is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R G is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R G is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0464] In ligand L A” In some embodiments where it is selected from List 10, at least one R H is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R H is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R His or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0465] In ligand L A” In some embodiments selected from List 10, 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.

[0466] In some embodiments, ligand L A” is selected from L A” w, where w is an integer from 1 to 463, and L A”1 through L A”463 each of which is defined in List 11 below:

[0467]

[0468]

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475]

[0476]

[0477]

[0478]

[0479]

[0480]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487] In some embodiments, the compound has the formula Ir(L A” ) p (L B ) q (L C ) r , where L B and L C are each bidentate ligands; and where p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p + q + r is the oxidation state of the metal M.

[0488] 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 where L A” , L B , and L C are different from each other.

[0489] In some embodiments, L B is a substituted or unsubstituted phenylpyridine, and L C is a substituted or unsubstituted acetylacetonate.

[0490] In some embodiments, the compound has the formula Pt(L A” )(L B ); and where L A” and L B can be the same or different. In some embodiments, L A” and LB Link to form a tetradentate ligand.

[0491] In some embodiments, L B and L C are each independently selected from the group consisting of: and the structures of Listing 5 as defined herein,

[0492] wherein:

[0493] T is selected from the group consisting of: B, Al, Ga, and In;

[0494] 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 ;

[0495] Y 1 to Y 13 each independently is selected from the group consisting of C and N;

[0496] 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 ;

[0497] R e and R f may be fused or joined to form a ring;

[0498] Each R a 、R b 、R c and R d independently represents mono-substituted to the maximum allowable number of substitutions or unsubstituted;

[0499] 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 consisting of the general substituents defined herein; and

[0500] R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d any two of the substituents may be fused or joined to form a ring or form a polydentate ligand.

[0501] In some embodiments, L B and L C each independently is selected from the group consisting of: and the structures of List 6 defined herein;

[0502] wherein:

[0503] 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 respective rings;

[0504] R a ’, R b ’, R c ’, R d ’ and R e ’ each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and

[0505] R a ’, R b ’, R c ’, R d ’ and R e ’ two of the substituents may be fused or joined to form a ring or form a polydentate ligand.

[0506] In some embodiments, the compound has the formula Ir(L A” )3, the formula Ir(L A” )(L Bk )2, the formula Ir(L A” )2(L Bk ), the formula Ir(LA” )2(L Cj-I ) or Ir(L A” )2(L Cj-II ),

[0507] where L A” according to any embodiment described herein, including L as defined in Listing 11 A”1 to L A”463 ;

[0508] where each L Bk has the structure of Listing 7 as defined herein;

[0509] where each L Cj-I has a structure based on the following formula: and

[0510] 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 the following Listing 12:

[0511]

[0512]

[0513]

[0514]

[0515]

[0516]

[0517]

[0518]

[0519]

[0520]

[0521]

[0522]

[0523] where R D1 to R D246 has the structure of the following Listing 13:

[0524]

[0525]

[0526]

[0527] In some embodiments, the compound is selected only from the group consisting of those compounds whose L Bk corresponds to one of the following: L B1 、L B30 、L B31 、L B109 、L B110 、L B112 、L B113 、L B114 、L B125 、L B127 、L B138 、L B140 、L B149 、L B150 、L B170 、L B171 、L B172 、L B174 、L B208 、L B241 、L B312 、L B315 、L B356 、L B367 、L B371 、L B382 、L B439 、L B440 、L B455 、L B456 、L B457 、L B458 、L B461 、L B462 、L B463 、L B469 and L B476 .

[0528] In some embodiments, the compound is selected only from the group consisting of those compounds whose L Bk corresponds to one of the following: L B1 、L B30 、L B31 、L B125 、L B138 、L B171 、L B172 、L B356 、L B357 、L B367, L B371 , L B382 , L B455 and L B456 .

[0529] In some embodiments, the compound is selected only from the group consisting of those compounds having an L Cj-I or an L Cj-II ligand, wherein the corresponding R 201 and R 202 are 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 , R D81 , R D87 , R D88 , R D89 , R D93 , R D116 , R D117 , R D118 , R D119 , R D120 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D147 , R D149 , R D151 , R D154 , R D155 , R D161 , R D175 , R D190 , R D193 , R D200 , R D201 , R D206, R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 and R D246 .

[0530] In some embodiments, the compound is selected only from the group consisting of those compounds having an L Cj-I or an L Cj-II ligand, wherein 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 .

[0531] In some embodiments, the compound is selected only from those compounds consisting of the group of compounds having one of the structures of Listing 14 for the L Cj-I ligand:

[0532]

[0533] 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 of Listing 9, Listing 10, and Listing 11, L B is selected from the group consisting of the structures of Listing 5, Listing 6, and Listing 7 (L Bk ), and L C is selected from the group consisting of the structures of L Cj-I and L Cj-II as defined herein.

[0534] In some embodiments, L A” is selected from the group consisting of the structures of Listing 9, and L B is selected from the group consisting of the structures of L Bk . In some embodiments, L A” is selected from the group consisting of the structures of Listing 10, and L B is selected from the group consisting of the structures of L Bk . In some embodiments, L A” is selected from the group consisting of the structures of Listing 11, and L B is selected from the group consisting of the structures of L Bk , where k is an integer from 1 to 530. In some embodiments, L A” is selected from Listing 11 as defined herein, and L C is selected from the group consisting of the structures of L Cj-I and L Cj-II , where j is an integer from 1 to 1416.

[0535] In some embodiments, the compound may have the formula Ir(L A”w)3, which consists of the following compounds: Ir(L A”1 )3 to Ir(L A”463 )3; the formula Ir(L A”w )(L B )2; the formula Ir(L A”w )2(L B ); the formula Ir(L A” )(L Bk )2; the formula Ir(L A” )2(L Bk ); the formula Ir(L A”w )(L Bk )2, which consists of the following compounds: Ir(L A”1 )(L B1 )2 to Ir(L A”463 )(L B530 )2; the formula Ir(L A”w )2(L Bk ), which consists of the following compounds: Ir(L A”1 )2(L B1 ) to Ir(L A”463 )2(L B530 ); the formula Ir(L A”w )2(L Cj-I ), which consists of the following compounds: Ir(L A”1 )2(L C1-I ) to Ir(L A”463 )2(L C1416-I ); the formula Ir(L A”w )2(L Cj-II ), which consists of the following compounds: Ir(L A”1 )2(L C1-II ) to Ir(L A”463 )2(L C1416-II ); the formula Ir(L A”w )(L Bk )(L Cj-I ), which consists of the following compounds: Ir(L A”1 )(L B1 )(L C1-I ) to Ir(L A”463 )(L B530 )(L C1416-I ); or the formula Ir(L A”w )(L Bk )(L Cj-II ), which consists of the following compounds: Ir(L A”1 )(L B1 )(L C1-II ) to Ir(L A”463 )(L B530 )(LC1416-II ), where L A”w , L Bk and L Cj-I and L Cj-II are all defined herein.

[0536] In some embodiments, the compound is selected from the group consisting of the structures of List 15 below:

[0537]

[0538]

[0539] In some embodiments, the compound of formula Ir(L A ) x (L B ) y (Lc) z or Ir(L A” ) p (L B ) q (L C ) r 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.

[0540] 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.

[0541] In the compound of formula Ir(L A ) x (L B ) y (Lc) z or Ir(L A” ) p (L B ) q (L C ) rIn some embodiments of the heteroleptic compound, ligand L A or L A” has a first substituent R I , wherein the first atom a-I in the first substituent R I is the farthest from the metal M among all the atoms in ligand L A . Additionally, ligand L B (if present) has a second substituent R II , wherein the first atom a-II in the second substituent R II is the farthest from the metal M among all the atoms in ligand L B . Furthermore, ligand L C (if present) has a third substituent R III , wherein the first atom a-III in the third substituent R III is the farthest from the metal M among all the atoms in ligand L C .

[0542] In such heteroleptic compounds, vectors V D1 , V D2 and V D3 can be defined as follows. V D1 represents the direction from the metal M to the first atom a-I, and the value D D1 of 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 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 vector V 3 represents the straight-line distance between the metal M and the first atom a-III in the third substituent R III .

[0543] 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 that allows the sphere to enclose all the atoms in the compound that are not part of the substituents R I , R II and R III ; and wherein at least one of D 1 , D 2 and D 3 is at least larger than the radius r. In some embodiments, D 1 , D2 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 greater than the radius r by at least In some embodiments, D 1 , D 2 and D 3 at least two of which 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 greater than the radius r by at least

[0544] In some embodiments of such heterocomplex 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 determined, wherein at least one of the angles between the transition dipole moment axis and the vectors V D1 , V D2 and V D3 is less than 40°. In some embodiments, at least one of the angles between the transition dipole moment axis and 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°.

[0545] 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°.

[0546] In some embodiments of such heterocomplex compounds, the compound has a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heterocomplex compounds, the compound has a VDR of 0.30, 0.25, 0.20 or 0.15 or less.

[0547] One of ordinary skill in the art will readily understand the meaning of the terms transition dipole moment axis of a compound and perpendicular 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.

[0548] 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 is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from the others). In some embodiments, when there is more than one ligand coordinated 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 other ligands. This also holds true in embodiments where the ligands coordinated to the metal can be linked to other ligands coordinated to the metal to form tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, in the case where the coordinated ligands are linked together, in some embodiments, all ligands can be the same, and in some other embodiments, at least one of the linked ligands can be different from the other ligands.

[0549] 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.

[0550] This disclosure encompasses any chemical structure that includes the novel compounds of this 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 referred to as supermolecules). As used herein, a "monovalent variant of a compound" refers to the same portion as the compound, but where one hydrogen has been removed and replaced with a bond that attaches to the remainder of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to the same portion as the compound, but where more than one hydrogen has been removed and replaced with one or more bonds that attach to the remainder of the chemical structure. In the case of supramolecules, the inventive compounds can also be incorporated into supramolecular complexes without covalent bonds. As used in this context, the description that structure A contains portion B means that structure A includes the structure of portion B, and the structure of portion B does not include H or D atoms that may be attached to portion B. This is because at least one H or D on the given portion structure must be replaced with a substituent such that portion 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 portion B structure can be further substituted.

[0551] C. OLEDs and Devices of the Present Disclosure

[0552] 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 portion of the present disclosure.

[0553] In some embodiments, the OLED includes: an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer contains a compound having the formula Ir(L A ) x (L B ) y (Lc) z or Ir(L A” ) p (L B ) q (L C ) r as defined herein.

[0554] 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.

[0555] In some embodiments, the organic layer may further comprise a host, wherein the host comprises 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-borata naphtho[3,2,1-de]anthracene, azaborinane, 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-borata naphtho[3,2,1-de]anthracene).

[0556] In some embodiments, the host may be selected from the group consisting of the structures in Host Group 1 below:

[0557]

[0558]

[0559]

[0560]

[0561]

[0562]

[0563]

[0564]

[0565]

[0566]

[0567] Wherein:

[0568] Each of J1 to J6 is independently C or N;

[0569] L’ is a direct bond or an organic linking group;

[0570] Each Y AA 、Y BB 、Y CC and Y DD is independently selected from the group consisting of: no bond, direct bond, O, S, Se, CRR’, SiRR’, GeRR’, NR, BR, BRR’;

[0571] 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;

[0572] Each R, R’, R A’ 、R B’ 、R C’ 、R D’ 、R E’ 、R F’ and R G’ is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring;

[0573] And, where possible, each unsubstituted aromatic carbon atom may be replaced by one or more N to form a nitrogen-containing substituted ring.

[0574] 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 is 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-containing ring.

[0575] 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:

[0576]

[0577]

[0578] The structures of MG1 to MG27 are shown as follows:

[0579] In the MGb structures 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.

[0580] In some embodiments, the host may be any one of its N - substituted 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 as defined in the following list of Host Group 2, where each of MGb, EGa, and Egc is defined as follows:

[0581]

[0582]

[0583] In the table above, 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 positions in the MGb structure.

[0584] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

[0585] 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 a 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).

[0586] In some embodiments, the compounds as described herein can be a sensitizer or a component of a sensitizer; wherein the device can further comprise a receptor that receives energy from the sensitizer. In some embodiments, the receptor is an emitter in the device. In some embodiments, the receptor 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 a receptor 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 excited - state complex that serves as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the receptor and the receptor will emit energy or further transfer the energy to a final emitter. The receptor concentration can range from 0.001% to 99.9%. The receptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the receptor is a thermally activated delayed fluorescence (TADF) material. In some embodiments, the receptor is a non - delayed fluorescence material. In some embodiments, the emission can be generated by any one or all of the sensitizer, the receptor, and the final emitter. In some embodiments, the emission of the receptor 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.

[0587] 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 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 the triplet and the singlet excited state. Thermal energy can activate the triplet transition 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.

[0588] In some embodiments, the OLED can comprise additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0589] In some embodiments, the inventive compounds described herein are phosphorescent materials.

[0590] 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 (e.g., a host material, an emitter material) within the OLED.

[0591] In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is an emitter that emits light within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material does not emit light within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material transfers its excited state energy to another material within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material participates in charge transport within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is a receptor, and the OLED further includes a sensitizer.

[0592] In some embodiments of the OLED, the delayed fluorescent material includes at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescent material is a metal complex. In some embodiments, the delayed fluorescent material is a non-metal complex. In some embodiments, the delayed fluorescent 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 fluorescent material includes a metal-carbene bond. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent 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-boraphenanthro[3,2,1-de]anthracene, 5λ 2 ,9λ 2 -diazabora-phenanthro[2,3,4-de]anthracene, 5-oxa-9λ 2-aza-13b-boraphenanthro[3,2,1-de]anthracene, azaborinane, oxaborole, dihydroacridine, 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, perylene, phenanthrene, fluorene, pyrene, perylene, and azulene.

[0593] 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 (Lc) z or Ir(L A” ) p (L B ) q (L C ) r 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 found 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 Parts A and D of the present disclosure.

[0594] 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.

[0595] 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 of light blue and dark blue 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.

[0596] In some embodiments, at least one pixel of the OLED or emissive region includes a total of N sub-pixels; wherein the N sub-pixels include a first sub-pixel and a second sub-pixel; wherein each of the N sub-pixels includes an emissive region; and wherein the total number of emissive regions within at least one pixel is equal to or less than N - 1. In some embodiments, the second emissive region is identical to the first emissive region; and each sub-pixel of at least one pixel includes one emissive region identical to the first emissive 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; wherein at least one display characteristic of the first pixel region is different from the corresponding display characteristic of the second pixel region, and wherein at least one display characteristic is selected from the group consisting of: resolution, cavity mode, color, out-coupling, and color filter.

[0597] 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 emissive region disposed above the first electrode, a first CGL disposed above the first emissive region, a second emissive region disposed above the first CGL, and a second electrode disposed above the second emissive region. In some embodiments, the first emissive region and / or the second emissive 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 emissive 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 emissive region is included in the sensitization device while the second emissive region is not included in the sensitization device; in some cases, both the first emissive region and the second emissive region are included in the sensitization device.

[0598] In some embodiments, the OLED can emit light with at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% from the plasmon mode. 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 comprises a plasmonic material that exhibits surface plasmon resonance, the plasmonic material being non-radiatively coupled to the emitter material and transferring 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 not exceeding a threshold distance from the organic emission layer, 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.

[0599] In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the side opposite to the organic emission layer above the enhancement layer. The outcoupling 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 mode, substrate mode, or another waveguide mode. In some embodiments, one or more intermediate layers can be disposed between the enhancement layer and the outcoupling 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.

[0600] 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, angular variation of emission intensity, 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 results in 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 OLEDs according to the present disclosure can further include any other functional layers common in OLEDs.

[0601] 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.

[0602] In some embodiments, the out-coupling layer has features of wavelength size or sub-wavelength size arranged periodically, quasi-periodically, or randomly. In some embodiments, the out-coupling layer may be composed of a plurality of nanoparticles. In some embodiments, the out-coupling layer is composed of a plurality of nanoparticles disposed on top of a material. In these embodiments, the out-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 out-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 out-coupling layer is formed by lithography.

[0603] 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.

[0604] In yet another aspect, the present disclosure also provides a consumer product that includes 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 include a compound or formulation of compounds as disclosed in the above compound portion of the present disclosure.

[0605] 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 having the formula Ir(L A ) x (L B ) y (Lc) z or Ir(L A” ) p (L B ) q (L C ) r as defined herein.

[0606] 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 through 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.

[0607] Figure 1 FIG. 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.

[0608] Additional instances of each of these layers can be obtained. For example, flexible and transparent substrate-anode combinations are 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 blocking layers 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 injection layers 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.

[0609] 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 layers can be omitted from the structure of the device 100.

[0610] 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 omitted altogether 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 host and 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, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials such as, for example, those described with respect to Figure 1 and 2 The different organic materials described.

[0611] 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.

[0612] 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 entirety), 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 entirety) 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 be suitable for the specific deposition method. For example, substituents such as alkyl and aryl groups that are branched or unbranched and preferably contain at least 3 carbons 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.

[0613] 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, vapors, 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 entireties.

[0614] 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 modules 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 which 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 certain types of visual displays. 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 transparent 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 comprising multiple displays tiled together, theater or stadium screens, light therapy devices, and signage. A variety of control mechanisms can be used to control 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).

[0615] 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.

[0616] 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.

[0617] 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 semi-transparent. 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 may be in the emission layer or in other functional layers, such as a down-conversion layer.

[0618] 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.

[0619] Other materials used in D.OLED

[0620] The materials described herein are various examples of materials that can be used in specific layers of 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.

[0621] a) Conductive dopants:

[0622] 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.

[0623] b) HIL / HTL:

[0624] 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 commonly 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 with conductive dopants; 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-hexaazatriphenylenehexanitrile; metal complexes; and crosslinkable compounds.

[0625] Examples of aromatic amine derivatives for HIL or HTL include (but are not limited to) the following general structures:

[0626]

[0627] 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.

[0628] In some embodiments, each Ar 1 to Ar 9 independently comprises a moiety selected from the group consisting of:

[0629]

[0630] 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.

[0631] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0632] 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.

[0633] In some embodiments, (Y 101 -Y 102 ) is a 2-phenylpyridine or 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.

[0634] 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 semi-conductive 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.

[0635] c) EBL:

[0636] 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 substantially 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 levels 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.

[0637] d) Host:

[0638] 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.

[0639] Examples of metal complexes used as hosts preferably have the following general formula:

[0640]

[0641] where 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.

[0642] In some embodiments, the metal complex is:

[0643]

[0644] where (O-N) is a bidentate ligand having a metal coordinated to O and N atoms.

[0645] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0646] 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, fluoranthene, 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, azadibenzothiophene, azadibenzofuran, azadibenzoselenophene, azacarbazole, azaindolocarbazole, azatriphenylene, azatetraphenylene, 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, 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. Each option within each group may be unsubstituted or may be substituted with a general substituent as described herein or may be further fused.

[0647] In some embodiments, the host compound comprises at least one selected from the moieties consisting of the following:

[0648] 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.

[0649] In some embodiments, the host material is selected from the group consisting of arylcarbazole, metal 8-hydroxyquinolinate (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).

[0650] e) Emitter materials in the EML:

[0651] 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 produce emission in a conventional OLED device. Examples of suitable emitter materials include, but are not limited to, compounds capable of producing 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.

[0652] In some embodiments, the emitter material has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0653] wherein L 1 , L 2 and L 3 can be the same or different;

[0654] wherein x is 1, 2 or 3;

[0655] wherein y is 0, 1 or 2;

[0656] wherein z is 0, 1 or 2;

[0657] wherein x + y + z is the oxidation state of the metal M;

[0658] wherein L 1 is selected from the group consisting of the structures in the following ligand list:

[0659]

[0660]

[0661] where each L 2 and L 3 are independently selected from the group consisting of and the structures in the ligand list; wherein: M is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu; T is selected from the group consisting of: B, Al, Ga, and In;

[0662] K 1’ is a direct bond or is selected from the group consisting of NR e 、PR e 、O, S, and Se;

[0663] Each Y 1 to Y 15 is independently selected from the group consisting of carbon and nitrogen;

[0664] 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 ;

[0665] Each R a 、R b 、R c and R d can independently represent mono-substituted to the maximum possible number of substitutions or unsubstituted;

[0666] 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 of general substituents as defined herein; and

[0667] where any two substituents can be fused or joined to form a ring or form a polydentate ligand.

[0668] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 1:

[0669]

[0670]

[0671]

[0672]

[0673] wherein

[0674] X 96 to X 99 each independently is C or N;

[0675] each Y 100 is independently selected from the group consisting of NR″, O, S, and Se;

[0676] R 10a , R 20a , R 30a , R 40a and R 50a each independently represents mono-substituted, up to maximum-substituted, or unsubstituted;

[0677] 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 independently is 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.

[0678] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 2:

[0679]

[0680]

[0681]

[0682]

[0683] wherein:

[0684] each Y 100 is independently selected from the group consisting of NR″, O, S, and Se;

[0685] 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;

[0686] X 100 and X 200 in each occurrence is independently selected from the group consisting of O, S, Se, NR″, and CR″R″′;

[0687] Each R A” 、R B” 、R C” 、R D” 、R E” and R F” independently represents mono-substituted, up to maximally substituted, or unsubstituted;

[0688] 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 of general substituents as defined herein; and any two substituents may be joined or fused to form a ring.

[0689] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom may be replaced by N to form a nitrogen 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, each Pt atom in the formula may be replaced by a Pd atom.

[0690] 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.

[0691] 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:

[0692]

[0693]

[0694] where A 1 -A 9 are each independently selected from C or N;

[0695] Each R P , R Q , and R U independently represents mono-substituted, up to maximum-substituted, or unsubstituted;

[0696] 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 is 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.

[0697] In some embodiments of the OLED, the delayed fluorescence material comprises at least one selected from the group of donor moieties consisting of:

[0698]

[0699]

[0700] where 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.

[0701] 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.

[0702] 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 moieties and donor moieties 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).

[0703] In some embodiments, the fluorescent material comprises at least one of chemical moieties selected from the group consisting of:

[0704]

[0705]

[0706] 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;

[0707] wherein X F and X G are each independently selected from the group consisting of C and N.

[0708] 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.

[0709] f) HBL:

[0710] 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. Additionally, 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.

[0711] In some embodiments, the compounds used in the HBL contain the same molecules or the same functional groups as those used in the host described above.

[0712] In some embodiments, the compounds used in the HBL comprise at least one of the following moieties selected from the group consisting of:

[0713] where k is an integer from 1 to 20; L 101 is another ligand and k' is an integer from 1 to 3.

[0714] g) ETL:

[0715] The electron transport layer (ETL) may include materials capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.

[0716] In some embodiments, the compounds used in the ETL contain at least one of the following moieties in the molecule:

[0717] 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.

[0718] In some embodiments, the metal complexes used in the ETL contain, but are not limited to, the following general formula:

[0719]

[0720] 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 connected to the metal.

[0721] In some embodiments, the ETL materials are 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.

[0722] h) Charge Generation Layer (CGL)

[0723] In a tandem or stacked OLED, the CGL plays a fundamental role in performance and is composed 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 electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductive dopants used in the transport layer.

[0724] In any of the compounds disclosed herein, hydrogen atoms may 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, deuterium atoms are attached to an aromatic ring. In some embodiments, deuterium atoms are attached to a saturated carbon atom, such as an alkyl or cycloalkyl carbon atom. In some other embodiments, deuterium atoms are attached to a heteroatom, such as an Si or Ge atom.

[0725] 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 may be replaced with 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.

[0726] E. Experimental Data

[0727] Synthesis of Representative Compound (Compound 1 of the Invention)

[0728]

[0729] A 500 mL four-necked flask equipped with a stir bar, condenser, thermocouple, and nitrogen inlet was charged with 4-(tert-butyl)-2-chloropyridine (4.6 g, 27.1 mmol, 1.0 equiv), 4,4,5,5-tetramethyl-2-(5,5,8,8-tetrakis(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)-1,3,2-dioxaborolane 1 (20.8 g, 62.4 mmol, 2.3 equiv), tripotassium phosphate monohydrate (17.3 g, 81.3 mmol, 3.0 equiv), toluene (193 mL), and ethanol (32 mL). The mixture was bubbled with nitrogen for 10 minutes. (Chloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II)) (XPhosPdG2) (0.43 g, 0.54 mmol, 0.02 equiv) was added, and the reaction mixture was then heated at reflux (ca. 87 °C) overnight. The reaction mixture was cooled to room temperature, concentrated, and the residue was combined with the residue from the previous run (ca. 2.95 mmol). The solution of the crude material in dichloromethane (300 mL) was filtered through a Celite pad (40 g) and rinsed with dichloromethane (20 mL) and ethyl acetate (2 × 40 mL). The filtrate was washed with water (100 mL) and then adsorbed onto (30 g). The adsorbed material was purified on a Biotage automated purification system (350 g HC Biotage silica cartridge) eluting with 1–15% ethyl acetate / hexanes to afford 4-(tert-butyl)-2-(5,5,8,8-tetrakis(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)pyridine 2 as a colorless oil containing residual hexanes (8.9 g, 87% yield).

[0730]

[0731] A 250 mL 3-necked flask equipped with a stirring bar, condenser, thermocouple and nitrogen inlet was charged with 4-(tert-butyl)-2-(5,5,8,8-tetra(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,4,6,6,7,7-d6)-pyridine (2) (6.8 g, 20.0 mmol, 2.1 equiv), 2-ethoxyethanol (70 mL) and DIUF water (18 mL). The reaction mixture was bubbled with nitrogen for 15 minutes. Iridium (III) chloride hydrate (3.0 g, 9.48 mmol, 1.0 equiv) was added to the reaction mixture, and the reaction mixture was then heated at reflux for 4 days. The reaction mixture was cooled to room temperature, filtered, and the solid was washed with methanol (30 mL). The solid was dried under vacuum at 60 °C for 6 h to give di-μ-chloro-tetrakis-[κ2(C2,N)-(4-(tert-butyl)-(2-(5,5,8,8-tetrakis(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,4,6,6,7,7-d6)-3′-yl)pyridin-1-yl]diiridium(III)3 (6.94 g, 80% yield, 98% LCMS purity, 82% 1 H-NMR purity).

[0732]

[0733] A 250 mL round bottom flask equipped with a stir bar, septum and nitrogen inlet was charged with di-μ-chloro-tetrakis[κ2(C2,N)-(4-(tert-butyl)-(2-(5,5,8,8-tetrakis(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,4,6,6,7,7-d6)-3'-yl)pyridin-1-yl]diiridium(III)3 (4.6 g, 2.54 mmol, 1.0 equiv), dichloromethane (40 mL) and methanol (10 mL). The reaction mixture was bubbled with nitrogen for 5 minutes. Silver trifluoromethanesulfonate (1.44 g, 5.59 mmol, 2.2 equiv) was added to the reaction mixture. The flask was then wrapped with foil to protect from light and the reaction mixture was then stirred at room temperature for 18 hours. The reaction mixture was passed through a silica gel (25 g) topped The mixture was filtered through a pad of 4-nitropropene (35 g), rinsed with dichloromethane (850 mL) and the filtrate was concentrated under reduced pressure. The solid was dried in vacuo at 55 °C to give [Ir(4-(tert-butyl)-(2-(5,5,8,8-tetrakis-(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,4,6,6,7,7-d6)-3'-yl)pyridin-1-yl)-(1H))2(MeOH)2] trifluoromethanesulfonate 4 (4.91 g, 89% yield, 96% LCMS purity) as a yellow solid.

[0734]

[0735] Into a 500 mL four-necked round-bottom flask equipped with a stirrer, a reflux condenser, and a thermocouple, charge [Ir(4-(tert-butyl)-(2-(5,5,8,8-tetrakis(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,4,6,6,7,7-d6)-3'-yl)pyridin-1-yl)-(1H))2(MeOH)2] trifluoromethanesulfonate 4 (6.71 g, 6.20 mmol, 1.1 equiv), 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[3,2-b]benzofuran-11-yl)pyridine 5 (2.45 g, 5.64 mmol, 1.0 equiv), and acetone (190 mL). Bubble the reaction mixture with nitrogen for 10 minutes. Add triethylamine (2.4 mL, 16.91 mmol, 3.0 equiv) to the reaction mixture, and then heat the reaction mixture under reflux in an inert atmosphere for 60 hours. Then photolyze the reaction mixture to obtain a crude reaction mixture. Concentrate the crude reaction mixture under reduced pressure. Subject the residue to column chromatography to obtain the compound 1 of the present invention as a yellow solid (2.67 g, 36% yield, 99.9% UPLC purity).

[0736] Synthesis of Example 2 of the Present Invention

[0737]

[0738] Add n-BuLi (1.6 M, 1.2 eq, 139.0 mL, 222.4 mmol) dropwise (over about 25 minutes) to a solution of 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (49.52 g, 1 eq, 185.30 mmol) in anhydrous THF (220 mL) at -78 °C (dry ice-acetone bath temperature). Stir the reaction mixture at -78 °C for 1 hour. Then add trimethyl borate (31 mL, 1.5 eq, 278.0 mmol). Allow the reaction mixture to warm slowly to room temperature and stir for another 2 hours. Slowly add 2 N HCl (300 mL). Extract the reaction mixture with EtOAc (3 × 50 mL) and dry over MgSO4. After filtration, concentrate the filtrate under a rotary evaporator to obtain the product 1' as a pale yellow oil, which solidifies upon standing (39.5 g, 92% yield).

[0739]

[0740] 2-Bromo-4-methoxybenzaldehyde (34.7 g, 1 eq, 161.4 mmol), (5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)boronic acid 1 (41.2 g, 1.1 eq, 177.5 mmol), Sphos-Pd-G2 (2.33 g, 0.02 eq, 3.23 mmol), and K3PO4 (68.5 g, 2 eq, 322.7 mmol) were added to a 500 mL round-bottom flask. Then, 1,4-dioxane (240 mL) and H2O (50 mL) were added, and the headspace of the flask was flushed with N2 for 10 minutes. The reaction mixture was then heated at 95 °C (oil bath temperature) under N2 overnight. After cooling to room temperature, NH4Cl (saturated aqueous solution, 100 mL) was added. The resulting organic layer was separated, the aqueous layer was extracted with CH2Cl2 (3 × 100 mL), and dried over MgSO4. After concentration in vacuo, the residue was purified on silica gel using CH2Cl2 / heptane (7 / 3) to give the desired compound 2' as a white solid (48.15 g, 93% yield, 99.7% LCMS purity).

[0741]

[0742] Add t BuOK (34.88 g, 2 eq, 310.9 mmol) was added to a solution of the Wittig salt (90.58 g, 1.7 eq, 264.2 mmol) in anhydrous THF (700 mL) at 0 °C (ice-water bath temperature). The reaction mixture was stirred at 0 °C for 2 hours, then a solution of 4-methoxy-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)benzaldehyde 2 (50.12 g, 1 eq, 155.4 mmol) in THF (190 mL) was added at 0 °C. The reaction mixture was then stirred at room temperature for 3 hours. Thin-layer chromatography (TLC) showed complete formation of the desired product. The reaction mixture was then quenched with H2O (500 mL) and extracted with CH2Cl2 (4 × 100 mL). After drying over MgSO4 and evaporation of the solvent, the residue was purified on silica gel using CH2Cl2 / heptane (3 / 7) to give the desired product 3' as a pale yellow oil (49.85 g, 92% yield).

[0743]

[0744] AlCl3 (28.44 g, 1.5 eq, 213.3 mmol) was added portionwise at room temperature to a solution of 6-(5-methoxy-2-(2-methoxyvinyl)phenyl)-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene 3 (49.85 g, 1 eq, 142.2 mmol) in 1,2-dichloroethane (500 mL). The reaction mixture was stirred at room temperature for 5 h. When TLC indicated completion of the reaction, the mixture was filtered through Celite and washed with CH2Cl2 (3 × 50 mL). After removal of the solvent in vacuo, the residue was purified on silica gel using CH2Cl2 / heptane (1 / 4) to afford 4’ as a pale yellow oil (25.38 g, 56% yield).

[0745]

[0746] A solution of 2-methoxy-8,8,11,11-tetramethyl-8,9,10,11-tetrahydrotetracene 4 (21.83 g, 1 eq, 68.55 mmol) in anhydrous THF (200 mL) was cooled to -78 °C (dry ice-acetone bath temperature). n-BuLi (2.5 M in hexanes, 1.8 eq, 49.4 mL, 123.4 mmol) was added dropwise at -78 °C (over ca. 15 min), and the reaction mixture was warmed to room temperature and stirred for 4 h. The reaction mixture was then cooled to -78 °C, 1,2-dibromoethane (13.6 mL, 2.3 eq, 157.7 mmol) was added dropwise (over ca. 10 min) and stirring was continued at -78 °C for 30 min, then warmed to room temperature and stirred for 1 h. The reaction mixture was quenched with NH4Cl (saturated aqueous solution, 100 mL) and extracted with CH2Cl2 (3 × 30 mL). After drying over MgSO4 and evaporation of the solvent, the residue was purified on silica gel using CH2Cl2 / heptane (1 / 9) to afford the desired product 5’ as a pale yellow solid (23.88 g, 88% yield).

[0747]

[0748] 3-Bromo-2-methoxy-8,8,11,11-tetramethyl-8,9,10,11-tetrahydrotetracene-5 (23.88 g, 1 eq, 60.10 mmol), (3-chloro-2-fluorophenyl)boronic acid (13.62 g, 1.3 eq, 78.13 mmol), Sphos-Pd-G2 (2.16 g, 0.05 eq, 3.00 mmol), and K3PO4 (25.51 g, 2 eq, 120.19 mmol) were added to a 500 mL round-bottom flask. Then, 1,4-dioxane (300 mL) and H2O (80 mL) were added, and the headspace of the flask was flushed with N2 for 10 minutes. The reaction mixture was then heated at 90 °C (oil bath temperature) under N2 overnight. After cooling to room temperature, NH4Cl (saturated aqueous solution, 100 mL) was added. The organic layer was separated, and the aqueous layer was extracted with CH2Cl2 (3 × 30 mL) and dried over MgSO4. After concentration in vacuo, the residue was purified on silica gel using CH2Cl2 / heptane (18% / 82%) to give the desired compound 6' as a white solid (24.18 g, 90% yield, 99% LCMS purity).

[0749]

[0750] BBr3 (12.8 mL, 2.5 eq, 135.2 mmol) was added dropwise to a solution of 3-(3-chloro-2-fluorophenyl)-2-methoxy-8,8,11,11-tetramethyl-8,9,10,11-tetrahydrotetracene-6 (24.18 g, 1 eq, 54.10 mmol) in CH2Cl2 (300 mL) at 0 °C (ice-water bath temperature), and the mixture was stirred at 0 °C for 30 minutes. The reaction mixture was then warmed to room temperature and stirring was continued for 4 hours. MeOH (50 mL) was slowly added at 0 °C (ice-water bath), and the mixture was extracted with CH2Cl2 (3 × 40 mL) and dried over MgSO4. After evaporation of the solvent, the residue was purified on silica gel using CH2Cl2 / heptane (3 / 2) to give the desired product 7' as a white solid (21.85 g, 93% yield).

[0751]

[0752] Representative procedure: Potassium carbonate (20.92 g, 3.0 eq, 151.4 mmol) was added to a 500 mL round-bottom flask containing a solution of 3-(3-chloro-2-fluorophenyl)-8,8,11,11-tetramethyl-8,9,10,11-tetrahydrotetracene-2-ol 7 (21.85 g, 1 eq, 50.47 mmol) in DMF (200 mL). The headspace of the flask was purged with N2 for 5 minutes. The reaction mixture was then heated at 120 °C (oil bath temperature) under N2 overnight. After cooling to room temperature, NH4Cl (saturated aqueous solution, 100 mL) and EtOAc (100 mL) were added, and the mixture was stirred for 20 minutes. The organic layer was separated, and the aqueous layer was extracted with CH2Cl2 (10 × 30 mL), EtOAc (5 × 30 mL), and dried over MgSO4. After concentration in vacuo, the residue was purified on silica gel with CH2Cl2 / heptane (15% / 85%) to give the desired compound 8' (18.58 g, 89% yield) as a white solid.

[0753]

[0754] In a 500 mL four-necked flask equipped with a stir bar, condenser, and thermocouple, 12-chloro-1,1,4,4-tetramethyl-1,2,3,4-tetrahydrotetracenobenzofuran (6.20 g, 1.0 equiv, 15.01 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (17.16 g, 4.5 equiv, 67.6 mmol), and potassium acetate (4.42 g, 3.0 eq, 45.04 mmol) were suspended in 1,4-dioxane (140.0 mL), and the mixture was bubbled with nitrogen for 5 minutes. Dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphane (493.1 mg, 0.08 equiv, 1.20 mmol) and tris(dibenzylideneacetone)dipalladium(0) (412.5 mg, 0.03 equiv, 450.4 μmol) were added, and the reaction mixture was heated at vigorous reflux for 4 hours. The solvent was evaporated to give a crude mixture of compound 9'. The crude mixture was used in the next step without further purification.

[0755]

[0756] The crude reaction mixture containing 9 was treated with deionized water (28 mL; pre-bubbled with nitrogen) and stirred for 10 minutes. Thereafter, 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (3.04 g, 1.0 equiv, 15.01 mmol), tripotassium phosphate (4.78 g, 1.5 equiv, 22.52 mmol) were added, and the mixture was bubbled with nitrogen for another 5 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.35 g, 0.02 equiv, 300.2 μmol) was added and the reaction mixture was heated under reflux for 18 hours. The reaction mixture was concentrated, the residue was diluted with DCM (500 mL) and washed with water (2 × 150 mL). The organic layer was filtered through filter paper, the filtrate was concentrated and subjected to column chromatography to give 10’ (6.05 g, 11.11 mmol, 74% yield).

[0757]

[0758] Compound 10 (3.1 g, 5.690 mmol), [Ir(4-(tert-butyl)-(2-phenyl-2′-yl)pyridin-1-yl)(-1H))2(MeOH)2] trifluoromethanesulfonate 11 (4.33 g, 1.0 equiv) and acetone (130 mL) were charged into a 250 mL four-necked flask equipped with a stir bar, condenser, nitrogen inlet and thermocouple. The suspension was bubbled with nitrogen. Triethylamine (2.4 mL, 3.0 equiv) was added and the mixture was heated at 51 °C overnight. After 20 hours, the reaction mixture was cooled and then concentrated. The residue was diluted in dichloromethane (60 mL) and passed through a pad of Celite (50 g). The Celite layer was washed with dichloromethane until all yellow color was removed (60 mL). The filtrate was concentrated and redissolved in dichloromethane (30 mL). Methanol (ca. 150 mL) was added and the solution was partially concentrated on a rotary evaporator until a thick slurry was formed. The solid was filtered off and air-dried to give the crude reaction mixture. Then the reaction mixture was photolyzed to give the desired product as a pale yellow solid (3.10 g, 2.68 mmol, 99.907%, 47% yield).

[0759] Device Examples

[0760] All exemplary devices were fabricated by thermal evaporation under high vacuum (<10 -7 Torr). The anode electrode was indium tin oxide (ITO). The cathode consisted of Liq (lithium 8-hydroxyquinoline) and thereafter Composition of Al. All devices were encapsulated with an epoxy-sealed glass lid immediately after fabrication in a nitrogen glove box (<1 ppm H2O and O2), while a desiccant was incorporated inside the package. The organic stack of the device example consisted, in sequence from the ITO surface, of: HAT-CN of as the hole injection layer (HIL); HTM of as the hole transport layer (HTL); thickness The emission layer (EML). The emission layer contained a 6:4 ratio of H-host (H1):E-host (H2) and 12 wt% of a green emitter. Liq (lithium 8-hydroxyquinoline) of doped with 35% ETM as the ETL. The device structure is shown in Table 1. Table 1 shows the schematic device structure. The chemical structures of the materials used in the test device are shown below.

[0761]

[0762] During fabrication, the EL and JVL of the device were measured and lifetime testing was carried out at DC 80 mA / cm 2 . The device performance data are shown in Table 2.

[0763] Table 1: Schematic device structure

[0764]

[0765] Table 2: Device performance

[0766]

[0767] * The voltage, LE, and EQE of Compound 1 of the present invention are reported as relative numbers normalized to the results of Comparative Compound 1.

[0768] The above data show that Compound 1 of the present invention exhibits a higher EQE (10% higher at 10 mA / cm 2 ) and a higher luminous efficiency (11% higher at 10 mA / cm 2 ) than Comparative Compound 1. Those values exceed any values attributable to experimental error and the observed improvement is significant and unexpected. Without being bound by any particular theory, it is assumed that this specific cycloalkyl chain modification in the dopant structure can increase the performance of the OLED device.

Claims

1. A compound having the formula Ir(L A ) x (L B ) y (Lc) z The compound in: L A It has the structure of formula IA: L B It has the structure of formula IB: L C It is a bidentate ligand; x is 1 or 2; y is 1 or 2; z is 0 or 1; and x+y+z=3; Formula II The structure is fused to at least one of moieties A, B, C or D; W 1 To W 8 Each of is independently C or N; Each of moiety A, moiety B, moiety C, and moiety D is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; and At least one of the following conditions is true: (1) at least one of moiety A or moiety B is a polycyclic fused ring system comprising at least four rings fused together; (2) at least one of moiety A or moiety B is a polycyclic fused ring system comprising at least three rings fused together, and R A '、R B '、R C '、R D ' and R E At least one of the groups independently comprises an electron-withdrawing group, a silane group or a germanium group; or (3) at least one of the moiety A or the moiety B is carbazole, aza-carbazole, fluorene or aza-fluorene; Where n is 1, 2 or 3; The dashed lines in Formula II represent direct bonds to two adjacent carbon atoms; R A '、R B '、R C '、R D ' and R E Each of the above independently represents mono-substitution to the maximum permissible substitution or no substitution; Each R A '、R B '、R C '、R D ' and R E 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 may be fused or joined to form a ring; and The compound is not 2. The compound according to claim 1, wherein the compound has the formula Ir(L A ) x (L B ) y , which has the structure of Formula I: in: x is 1 and y is 2, or x is 2 and y is 1.

3. The compound of claim 1, wherein each of moiety A, moiety B, moiety C, and moiety D is independently selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiazole phenanthrene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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 at least one R which is not part of formula II A 'contains a substituent selected from alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof; and / or at least one R which is not part of Formula II B 'contains a substituent selected from alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof; and / or at least one R which is not part of Formula II C 'contains a substituent selected from alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof; and / or at least one R which is not part of Formula II D 'contains a substituent selected from alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof; and / or at least one R which is not part of Formula II E Contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

4. The compound according to claim 1, wherein the ligand L A Select from the group consisting of: in: Z 7 To Z 16 Each of is independently C or N; YSelect from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,C=S,C=Se,S=O,SO2,C=CR e R f 、C=NR e , CR e R f 、P(O)R e 、SiR e R f and GeR e R f ; Y1 is selected from the group consisting of: B, N, P, CR e 、SiR e and GeR e ; R AA and R BB Each of the above independently represents mono-substitution to the maximum permissible substitution or no substitution; Each R AA , R BB , R N , R e and R f 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, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Any two substituents may be fused or joined to form a ring; or The ligand L A Select from the group consisting of: in: X1 to X 19 each independently is C or N; Y1, Y A , Y B and Y C 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 and GeR e R f ; Each R A1 , R B1 , R B2 and R B3 independently represents mono-substitution to the maximum possible number of substitutions or no substitution; Each R A1 , R B1 , R B2 , R B3 , R e and R f 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, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Any two substituents may be fused or joined to form a ring; or The ligand L A Select from the group consisting of: in: Each of X and Y is independently selected from the group consisting of: BR e NR e , PR e , O, S, Se, C=O, C=S, C=Se, S=O, SO2, C=CR e R f 、C=NR e , CR e R f 、P(O)R e 、SiR e R f and GeR e R f ; R AA , R BB and R C Each of the above independently represents mono-substitution to the maximum permissible substitution or no substitution; Each R AA , R BB , R C , R e , R f and R N 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, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Any two substituents may be fused or joined to form a ring.

5. The compound according to claim 1, wherein the ligand L A Selected from L Ai , where i is an integer from 1 to 420, and L A1 To L A420 Each of them is defined in Listing 4 below: The ligand L A Selected from L A'w (G A )(R H )(R I )(R J )(R K ), wherein w is an integer from 1 to 72, and R H , R I , R J and R K Each of which is independently selected from the group consisting of V1 to V148; G A is selected from G1 to G57; and L A'1 (G1)(V1)(V1)(V1)(V1) to L A'72 Each of (G57)(V148)(V148)(V148)(V148) is defined in the following 3a list: Where each of V1 to V148 is defined as follows: and Where each of G1 to G57 is defined as follows: The ligand L A Selected from L A*w’ (R H )(R I )(R J )(R K ), wherein w' is an integer from 1 to 28, and R H , R I , R J and R K Each of which is independently selected from the group consisting of V1 to V148; and L A*1 (V1)(V1)(V1)(V1) to L A*28 Each of (V148)(V148)(V148)(V148) is defined in Listing 3b:

6. The compound according to claim 5, wherein L A Can be selected from L Ai , or L A'w (G A )(R H )(R I )(R J )(R K ), or L A*w' (R H )(R I )(R J )(R K );and L B You can choose from the following groups:

7. An Ir complex having formula III: The structure of ligand L A” ,in: The moiety F 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 To X 10 Each of is independently C or N; Y A 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'; Formula II The structure is fused to ring H or ring G; n is 1, 2, or 3; The dashed lines in Formula II represent direct bonds to two adjacent carbon atoms; R E , R F , R G and R H Each of the above independently represents mono-substitution to the maximum permissible substitution or no substitution; Each R, R', R E , R F , R G and R H 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; and Any two substituents may be fused or joined to form a ring, provided that if Ring F is pyridine, then each of the following is true: Any two R substituents bonded to the same carbon atom are identical; R E It’s not fluorine; If two R E are bonded to the same carbon, then they do not join to form a spiro center; and Formula II does not contain X 6 and X 7 Condensed.

8. The compound according to claim 7, wherein X 1 To X 8 Each of which is carbon or where X 1 To X 8 each of which is N; and / or wherein Y A selected from the group consisting of O, S and Se; and / or wherein the moiety F is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbenes, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzene thiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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 At least one of the R F comprising a substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and a combination thereof; and / or wherein at least one R G comprising a substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and a combination thereof; and / or wherein at least one R H comprising a substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and a combination thereof; and / or wherein at least one R E Contains a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

9. The compound according to claim 7, wherein the ligand L A” Selected from the group consisting of the following structures of Listing 9: in: X 11 To X 14 Each of is independently C or N; YSelect from the group consisting of: BR e NR e , PR e , O, S, Se, C=O, C=S, C=Se, S=O, SO2, C=CR e R f 、C=NR e , CR e R f 、P(O)R e 、SiR e R f and GeR e R f ; Y1 is selected from the group consisting of: B, N, P, CR e 、SiR e and GeR e ; Each R N , R e and R f 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, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Any two substituents may be fused or joined to form a ring; or The ligand L A” You can select from the group consisting of the following structures in Listing 10: in: Y A and Y B Each of which is selected from the group consisting of: BR e NR e , PR e , O, S, Se, C=O, C=S, C=Se, S=O, SO2, C=CR e R f 、C=NR e , CR e R f 、P(O)R e 、SiR e R f and GeR e R f ; R e and R f may be fused or joined to form a ring; R F , R G and R H Each of the above independently represents mono-substitution to the maximum permissible substitution or no substitution; R N , R F , R G and R H Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and Any two substituents may be fused or joined to form a ring; or The ligand L A” Optional free structure L A”1 To L A”463 The group is defined in the following Listing 11:

10. The compound according to claim 7, wherein the compound has the formula Ir(L A” ) p (L B ) q (L C ) r , where L B and L C Each is a bidentate ligand; and wherein p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; and p+q+r is the oxidation state of the metal M.

11. The compound according to claim 10, wherein the compound has a formula Ir(L) selected from the group consisting of 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 where L A" , L B and L C Different from each other; or formula Pt(L A” )(L B ); and where L A” and L B Can be the same or different.

12. The compound according to claim 10, wherein L B and L C Each independently selected from the group consisting of: And the structure of Listing 5 below: 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 may be fused or joined to form a ring; Each R a , R b , R c and R d independently represents monosubstituted to the maximum permissible 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 may be fused or joined to form a ring or to form a multidentate ligand.

13. The compound according to claim 10, wherein the compound has the formula Ir(L A” )3, Formula Ir(L A” )(L Bk )2, Formula Ir(L A” )2(L Bk ), formula Ir(L A” )2(L Cj-I ) or formula Ir(L A” )2(L Cj-II ), Where k is an integer from 1 to 630, and each L Bk With the following structure defined in Listing 7: Each L Cj-I Has a structure based on the formula: and Each L Cj-II Has a structure based on the following formula: For L Cj-I and L Cj-II Each L Cj , R 201 and R 202 As defined below: Where R D1 To R D246 Has the following structure:

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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