Organic electroluminescent materials and devices

Abstract

To provide novel organometallic compounds.SOLUTION: Provided is a compound including ligand LA of the following Formula I, wherein ring A and ring B are each independently a 5- or 6-membered carbon ring or heterocycle; Z1 to Z5 are each independently C or N; X is BR1, and the like; Y is NR3, and the like; and RA, RB, R1, and R3 are each independently H, D, halogen, alkyl, cycloalkyl, and the like.SELECTED DRAWING: None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 62 / 859,433, filed June 10, 2019, the disclosure of which is incorporated herein by reference in its entirety. This application is also a continuation-in-part of U.S. Patent Application No. 16 / 217,467, filed December 12, 2018, the disclosure of which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE DISCLOSURE This disclosure relates generally to organometallic compounds and compositions and their various uses, including as light emitters in devices such as organic light emitting diodes and related electronic devices. [Background technology]

[0003] Optoelectronic devices that utilize organic materials are becoming increasingly desirable for a variety of reasons. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as flexibility, may make them well suited 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 may have performance advantages over traditional materials.

[0004] OLEDs utilize thin organic films that emit light when a voltage is applied across the device and are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting and backlighting.

[0005] One application of phosphorescent emissive molecules is full color displays. Industry standards for such displays require pixels adapted to emit specific colors, referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. Conventional liquid crystal display emission from a white backlight is filtered with absorbing filters to produce red, green, and blue emission. Similar techniques can be used with OLEDs. White OLEDs can be either single emissive layer (EML) devices or stack structures. Color can be measured using CIE coordinates, which are well known in the art. Summary of the Invention

[0006] In one aspect, the present disclosure provides a ligand L of formula I: A The present invention provides a compound comprising: [ka] In the formula, ring A and ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; 1 ~Z 5 are each independently C or N; X is BR 1 , B.R. 1 R 2 , AlR 1 , AlR 1 R 2 , GaR 1 , GaR 1 R 2 ,InR 1 ,InR 1 R 2 , CO, SO 2 , or POR 1 and Y is NR 3 , N.R. 3 R 4 , P.R. 3 , O, S, SO, SO 2 , C.R. 3 R 4 , SiR 3 R 4 , P.R.3 R 4 , or GeR 3 R 4 ;R A and R B each represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R A , R B , R 1 , R 2 , R 3 , and R 4 each is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents can be bonded or fused together to form a ring, and said ligand L A is coordinated to the metal M by two labeled wavy lines; the ligand L A can be combined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands.

[0007] In another aspect, the present disclosure provides a ligand L of formula I as described herein. A The present invention provides a composition of matter comprising:

[0008] In yet another aspect, the present disclosure provides a ligand L of formula I as described herein. A The present invention provides an OLED having an organic layer comprising a compound comprising:

[0009] In yet another aspect, the present disclosure provides a ligand L of formula I as described herein. A The present invention provides a consumer product that includes an OLED having an organic layer that includes a compound comprising: [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 shows an organic light emitting device.

[0011] [Diagram 2] FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] A. Terminology Unless otherwise stated, the following terms used herein are defined as follows.

[0013] As used herein, the term "organic" includes polymeric and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" can actually be quite large. Small molecules can include repeat units in some circumstances. For example, the use of long chain alkyl groups as a substituent does not remove a molecule from the "small molecule" class. Small molecules can be incorporated into polymers, for example, as pendant groups on a polymer backbone or as part of the backbone. Small molecules can also serve as the core moiety of dendrimers, which consist of a series of chemical shells built on the core moiety. The core moiety of a dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

[0014] As used herein, "top" means furthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as "disposed over" a second layer, the first layer is disposed further from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode may be described as "disposed over" an anode, even though there may be various organic layers in between.

[0015] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium, either in the form of a solution or suspension.

[0016] A ligand may be referred to as "photoactive" if it is believed that the ligand directly contributes to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" if it is believed that the ligand does not contribute to the photoactive properties of the emissive material, although the ancillary ligand may modify the properties of the photoactive ligand.

[0017] As used herein, and as generally understood by those skilled in the art, a first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IPs) are measured as negative energies relative to the vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (a less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of such a diagram than a "lower" HOMO or LUMO energy level.

[0018] As used herein, as generally understood by those skilled in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work functions are generally measured as negative numbers relative to the vacuum level, this means that a "higher" work function is more negative. In a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being further away from the vacuum level in a downward direction. Thus, the definition of the HOMO and LUMO energy levels follows a different convention than work functions.

[0019] The terms "halo," "halogen," and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0020] The term "acyl" refers to a substituted carbonyl group (C(O)-R s )

[0021] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s Or -C(O)-OR s ) group.

[0022] The term "ether" means -OR s Refers to the base.

[0023] The terms "sulfanyl" and "thioether" are used interchangeably, and -SR s Refers to the base.

[0024] The term "sulfinyl" refers to -S(O)-R s Refers to the base.

[0025] The term "sulfonyl" means -SO 2 -R s Refers to the base.

[0026] The term "phosphino" refers to -P(R s ) 3 Each R s may be the same or different.

[0027] The term "silyl" means -Si(R s ) 3 Each R s may be the same or different.

[0028] The term "boryl" means -B(R s ) 2 group, or its Lewis adduct -B(R s ) 3 R refers to the group s may be the same or different.

[0029] In each of the above, Rs can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0030] The term "alkyl" refers to and includes both straight and branched chain alkyl groups. Preferred alkyl groups contain from 1 to 15 carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, and 2,2-dimethylpropyl. Additionally, the alkyl groups may be optionally substituted.

[0031] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing from 3 to 12 ring carbon atoms, including cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl groups may be optionally substituted.

[0032] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Furthermore, the heteroalkyl group or the heterocycloalkyl group may be optionally substituted.

[0033] The term "alkenyl" refers to and includes both straight-chain and branched-chain alkene groups. An alkenyl group is essentially an alkyl group containing at least one carbon-carbon double bond in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group containing at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkenyl, cycloalkenyl, or heteroalkenyl groups may be optionally substituted.

[0034] The term "alkynyl" refers to and includes both straight and branched chain alkyne groups. An alkynyl group is essentially an alkyl group that contains at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those that contain 2 to 15 carbon atoms. Additionally, said alkynyl groups may be optionally substituted.

[0035] The terms "aralkyl" and "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group, which may be optionally substituted.

[0036] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Heteroaromatic cyclic groups may be used interchangeably with heteroaryl. Preferred hetero non-aromatic cyclic groups are those containing 3-7 ring atoms and contain at least one heteroatom, including cyclic amines such as morpholino, piperidino, pyrrolidino, and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Furthermore, the heterocyclic groups may be optionally substituted.

[0037] The term "aryl" refers to and includes both monocyclic aromatic hydrocarbyl groups and polycyclic aromatic ring systems. A polycyclic ring can have two or more rings with two carbons shared between two adjacent rings (the rings being "fused"), at least one of the rings being an aromatic hydrocarbyl group, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably those containing 6 to 20 carbon atoms, and more preferably those containing 6 to 12 carbon atoms. Aryl groups having 6 carbons, 10 carbons, or 12 carbons are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, and are preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Furthermore, the aryl group may be optionally substituted.

[0038] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems containing at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Heteromonocyclic aromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings can have 1 to 6 heteroatoms. Heteropolycyclic ring systems can have two or more rings in which two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is heteroaryl, e.g., the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Heteropolycyclic aromatic ring systems can have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably those containing 3 to 20 carbon atoms, and more preferably those containing 3 to 12 carbon atoms.Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benziso ... Examples of heteroaryl groups include benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, with dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza analogs thereof being preferred. Furthermore, the heteroaryl groups may be optionally substituted.

[0039] Of the aryl and heteroaryl groups listed above, the triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole groups, and their respective aza analogues, are of particular interest.

[0040] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl are independently unsubstituted or independently substituted with one or more common substituents.

[0041] In many instances, the typical substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.

[0042] In some instances, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.

[0043] In some instances, more preferred common substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.

[0044] In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0045] The terms "substituted" and "substituted" refer to a substituent other than H attached to the relevant position (e.g., carbon or nitrogen). For example, R 1 If represents a monosubstitution, one R 1 must be other than H (i.e., a substitution). Similarly, R 1 If represents a disubstitution, R 1 must be other than H. Similarly, R 1 When R represents zero or no substitution, 1can be hydrogen at an available valence of a ring atom, as in the case of carbon atoms in benzene and nitrogen atoms in pyrrole, or simply represents nothing in the case of ring atoms with fully filled valences (e.g., nitrogen in pyridine). The maximum number of substitutions possible in a ring structure depends on the total number of available valences on the ring atoms.

[0046] As used herein, "combinations thereof" refers to one or more members of the applicable list being combined to form a known or chemically stable configuration that one of skill in the art can envision from the applicable list. For example, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl group; halogen and alkyl can be combined to form a halogenated alkyl substituent; halogen, alkyl, and aryl can be combined to form a halogenated aryl alkyl. In one example, the term substituted includes combinations of 2-4 of the listed groups. In another example, the term substituted includes combinations of 2-3 groups. In yet another example, the term substituted includes combinations of 2 groups. Preferred combinations of substituents include those that contain up to 50 atoms that are not hydrogen or deuterium, or those that contain up to 40 atoms that are not hydrogen or deuterium, or those that contain up to 30 atoms that are not hydrogen or deuterium. In many examples, preferred combinations of substituents include up to 20 atoms that are not hydrogen or deuterium.

[0047] The designation "aza" in the fragments described herein, such as aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in each aromatic ring can be replaced by a nitrogen atom, for example, but not by way of limitation, azatriphenylene includes both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of skill in the art can easily imagine other nitrogen analogs of the above-mentioned aza derivatives, and all such analogs are intended to be encompassed by the terms described herein.

[0048] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, International Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. 2011 / 0037057, the contents of which are incorporated by reference in their entirety, describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Tetrahedron 2015, 71, 1425-30 (Ming Yan et al.) and Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65 (Atzrodt et al.), the contents of which are incorporated by reference in their entirety, which describe efficient routes for the deuteration of methylene hydrogens in benzylamines and the replacement of aromatic ring hydrogens with deuterium, respectively.

[0049] It is understood that when a molecular fragment is described as being a substituent or attached to another moiety, the name may be described as being the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). Different designations of the substituents or attached fragments are considered equivalent herein.

[0050] In some cases, the adjacent substituents of a pair can be optionally bonded or fused to form a ring. Preferred rings are 5-, 6-, or 7-membered carbocyclic or heterocyclic rings, including both cases where the portion of the ring formed by the pair of substituents is saturated and cases where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two related substituents can be on the same ring adjacent to each other, or on the two adjacent rings with the two nearest available substitutable positions, such as 2- and 2'-positions in biphenyl and 1- and 8-positions in naphthalene, as long as a stable fused ring system can be formed. B. Compounds of the Present Disclosure

[0051] In one aspect, the present disclosure provides a ligand L of formula I: A The present invention provides a compound comprising: [ka] wherein ring A and ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; Z 1 ~Z 5 are each independently C or N; X is BR 1 , B.R. 1 R 2 , AlR 1 , AlR 1 R 2 , GaR 1 , GaR 1 R 2 ,InR 1 ,InR 1 R 2 , CO, SO 2 , or POR 1 and; Y is NR 3 , N.R. 3 R 4 , P.R. 3 , O, S, SO, SO 2 , C.R. 3 R 4 , SiR 3 R 4 , P.R. 3 R 4 , or GeR 3 R 4 and; R A and R B each represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R A , R B , R 1 , R 2 , R 3 , and R 4 each is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; Any two substituents may be bonded or fused together to form a ring; Said ligand L A is coordinated to the metal M by two labeled wavy lines; Said ligand L A can be combined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands.

[0052] In some embodiments, R A and R B Each of may be independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

[0053] In some embodiments, M can be selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au. In some embodiments, M can be selected from the group consisting of Os, Ir, Pd, and Pt. In some embodiments, M can be Ir. In some embodiments, M can be Pt.

[0054] In some embodiments, the ligand L A can have the formula IA: [ka] During the ceremony Z 1 ~Z 4 at least two of are C; X is BR 1 and Y is NR 3 or O, or X is BR 1 R 2 and Y is NR 3 R 4 and; R 1 , R2 , R 3 , and R 4 each is independently selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, silyl, boryl, aryl, heteroaryl, alkoxy, aryloxy, amino, and combinations thereof; The remaining variables are the same as previously defined in Formula I. Said ligand L Aa can combine with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; X is BR 1 and Y is NR 3 When BR 1 R 1 But NR 3 R 3 Two substituents can be linked to form a ring, except that they do not form a ring with .

[0055] With respect to formula IA, in some embodiments, R A and R B Each of can be independently hydrogen or a substituent selected from the group consisting of generic substituents defined herein. In some embodiments, X is BR 1 and Y can be NR 3 In some embodiments, R 1 and R 3 Each of may be selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. 1 R 1 can have the following formula II: [ka] wherein ring C is a 5- or 6-membered carbocyclic or heterocyclic ring; Z 6 , Z 7 , and Z 8 are each independently C or N; R Xis R in formula I A or R B has the same definition as; 5 and R 6 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; R 5 and R 6 At least one of R is not hydrogen. In some of the above embodiments, ring C can be a benzene ring. In some of the above embodiments, R 5 and R 6 are each independently hydrogen, methyl, or CD 3 , ethyl, isopropyl, isobutyl, tert-butyl, cyclohexyl, and substituted or unsubstituted phenyl.

[0056] With respect to formula IA, in some embodiments, Y is NR 3 R 3 is alkyl, cycloalkyl, aryl, or heteroaryl. In some embodiments, ring A can be a 5-membered heterocycle. In some embodiments, ring B can be a 6-membered carbocycle or heterocycle. In some embodiments, Z 1 and Z 3 can be N, Z 2 and Z 4 can be C. In some embodiments, X is BR 1 and Y can be NR 3 Z can be 3 can be N, and ring A can be a 5-membered ring.

[0057] In some embodiments, the ligand L A can be selected from the group consisting of: [ka] [ka] [ka] [ka] In the formula, R Z and R C is R in formula I A has the same definition as; 7 ~R 17 is R in formula IA 1 It has the same definition as

[0058] In some embodiments of the compounds, the ligand L A can be selected from the group consisting of the structures in LA List 1 below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] R in the formula A i,R A j, R A k, R A l, R A m, R A n, R A o, R A p, R A q, R A r, R A x, R A y, and R A z has the structure defined in RA Listing 1 below. [ka] [ka] [ka] L Q s, L Q t, L Q u, L Q v, and L Q w has the structure defined in LQ Listing 1 below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0059] In some embodiments of the compounds, the ligand L A is expressed by the following formula IB [ka] and During the ceremony, X 1 , X 2 , and X 3 are each independently C or N, and at least two of them are C; Z 1 and Z 5 one is C and the other is N; The remaining variables are the same as previously defined in Formula I.

[0060] With reference to formula IB, in some embodiments, R A and R B Each of X is independently hydrogen or selected from the group consisting of preferred general substituents defined herein. 1 R 2 In some embodiments, R 1 and R 2 may each independently be fluorine, alkyl, cycloalkyl, aryl, heteroaryl, or a combination thereof. In some embodiments, R 1 and R 2 can each independently be F. In some embodiments, Y is NR 3or O. In some embodiments, R 3 can be alkyl, cycloalkyl, aryl, heteroaryl, or a combination thereof. In some embodiments, X 1 , X 2 , and X 3 may each independently be C. In some embodiments, Z 1 can be N, Z 5 can be C. In some embodiments, ring B can be a 6-membered aromatic ring. In some embodiments, ring B can be benzene, pyridine, pyrazine, pyrimidine, or triazine. In some embodiments, ring B can be benzene. In some embodiments, two adjacent R A The substituents can be linked to form a fused ring. In some embodiments, two adjacent R B The substituents can be linked to form a fused ring. In some embodiments, the fused ring can be a six-membered aromatic ring. In some embodiments, the fused ring can be benzene or pyridine.

[0061] Ligand L having formula IB A In some embodiments, the ligand L A can be selected from the group consisting of: [ka] [ka] In the formula, Y 1 are O, S, and NR 3 , P.R. 3 , C.R. 3 R 4 , or SiR 3 R 4 and the remaining variables are the same as previously defined.

[0062] Ligand L having formula IB AIn some embodiments, the ligand L A can be selected from the group consisting of structures defined in LA List 2 below. [ka] [ka] [ka] [ka] [ka] In the formula, R A i,R A j, and R A k has the structure defined below. [ka]

[0063] In some of the above embodiments, the compound has the formula M(L A )x(L B )y(L C )z, where L A is a ligand described as having formula I, formula IA, or formula IB; L B and L C are each a bidentate ligand; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M.

[0064] In some of the above embodiments, the compound is Ir(L A ) 3 , Ir(L A )(L B ) 2 , Ir(L A ) 2 (L B ), Ir(L A ) 2 (LC ), and Ir(L A )(L B )(L C ) wherein L A , L B , and L C are different from each other.

[0065] In some of the above embodiments, the compound has the formula Pt(L A )(L B ) in which L A and L B may be the same or different. In some of these embodiments, L A and L B can be linked to form a tetradentate ligand.

[0066] In some of the above embodiments, L B and L C may each independently be selected from the group consisting of: [ka] [ka] During the ceremony, Y 1 ~Y 13 each is independently selected from the group consisting of C and N; Y' is BR e , N.R. e , P.R. e , O, S, Se, C=O, S=O, SO 2 , C.R. e R f , SiR e R f , and GeR e R f wherein R e and R f can be fused or linked to form a ring; R a , R b , R c, and R d each independently represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R a , R b , R c , R d , R e , and R f each is independently hydrogen or selected from the group consisting of the generic substituents described herein; R a , R b , R c , and R d Any two adjacent substituents of can be fused or linked to form a ring or to form a multidentate ligand.

[0067] In some of the above embodiments, L B and L C may each independently be selected from the group consisting of: [ka] [ka] [ka] [ka] During the ceremony, R a ', R b ', and R c each ' independently represents zero, mono, or up to the maximum number of substitutions allowed on the associated ring; R a , R b , R c , R N , R a ', R b ', and R c Each of ' is independently hydrogen or a substituent selected from the group consisting of generic substituents described herein; Ra ', R b ', and R c Two adjacent substituents of may be fused or linked to form a ring or to form a multidentate ligand.

[0068] In some embodiments, the compound has the formula Ir(L A ) 3 , Formula Ir(L A )(L B ) 2 , Formula Ir(L A ) 2 (L C ), or formula Ir(L A )(L B )(L C ), wherein L A has formula I, formula IA, or formula IB; L B is selected from the first LB list described herein, and L C is selected from the first LC list described herein.

[0069] In some embodiments, the compound has the formula Ir(L A ) 3 , Formula Ir(L A )(L B ) 2 , Formula Ir(L A ) 2 (L C ), or formula Ir(L A )(L B )(L C ), wherein L A is a ligand having the formula IA, L B is selected from the first LB list described herein, and L C is selected from the first LC list described herein.

[0070] In some embodiments, the compound has the formula Ir(L A ) 3 , Formula Ir(L A )(L B ) 2 , Formula Ir(L A )2 (L C ), or formula Ir(L A )(L B )(L C ), wherein L A is a ligand having the formula IB, L B is selected from the first LB list described herein, and L C is selected from the first LC list described herein.

[0071] If the compound has the formula M(L A ) x (L B ) y (L C ) z In some of the above embodiments having L A can be any of the embodiments defined above, and L B can be selected from the LB list 1 consisting of: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] In the formula, L C has the following structure: [ka] Based on L Cj-I and the following structure: [ka] Based on L Cj-II wherein j is an integer from 1 to 768; and L Cj-I and L Cj-II Each L in Cj In the case of R 1’ and R 2’ is defined as shown in LC Listing 1 below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] In the formula, R D1 ~R D192 has the following structure: [ka] [ka] [ka]

[0072] L B In some of the above embodiments, L is selected from the group consisting of the first LB list. B can be selected from the group consisting of: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B130 , L B32 , L B134 , L B136 , L B138 , L B140 , L B142 , L B144 , L B156 , L B58 , L B160 , L B162 , L B164 , L B168 , L B172 , L B175 , L B204 , L B206, L B214 , L B216 , L B218 , L B220 , L B222 , L B231 , L B233 , L B235 , L B237 , L B240 , L B242 , L B244 , L B246 , L B248 , L B250 , L B252 , L B254 , L B256 , L B258 , L B260 , L B262 , L B263 , L BB1 , L BB2 , L BB3 , L BB4 , L BB5 , L BB6 , L BB7 , L BB8 , L BB9 , L BB10 , L BB11 , L BB12 , L BB13 , L BB14 , L BB15 , L BB16 , L BB17 , L BB18 , L BB20 , L BB22 , L BB24 , L BB34 , L BB37 , L BB71 , L BB74 , L BB88 , L BB90 , L BB97 , L BB103 , L BB104 , L BB105 , L BB106 , L BB107 , L BB112 , L BB113 , L BB115 , L BB16 , L BB117 , L BB118 , L BB119 , L BB121 , L BB122 , and L BB123 .

[0073] L B In some of the above embodiments, L is selected from the group consisting of the first LB list. B can be selected from the group consisting of: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B132 , L B136 , L B138 , L B142 , L B156 , L B162 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B231 , L B233 , L B237 , L BB1 , L BB2 , L BB3 , L BB4 , L BB5 , L BB6 , L BB13 , L BB14 , L BB18 , L BB20 , L BB22 , L BB24 , L BB34 , L BB37 , L BB103 , L BB104 , L BB105 , L BB106 , L BB107 , L BB113 , L BB115 , L BB16 , and L BB121 .

[0074] L C In some of the above embodiments, L is selected from the group consisting of the first LC list. C is the corresponding R 1’ and R 2’are each independently selected from the following structures, L Cj-I and L Cj-II The compound may be selected from the group consisting of: [ka]

[0075] L C In some of the above embodiments, L is selected from the group consisting of the first LC list. C is the corresponding R 1’ and R 2’ are each independently selected from the following structures, L Cj-I and L Cj-II The compound may be selected from the group consisting of: [ka]

[0076] In some of the above embodiments, L C can be selected from the group consisting of: [ka] [ka]

[0077] In some embodiments, the compound can be selected from the group consisting of the structures in Compound List 1 below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0078] In some embodiments, the compound can have the structure of Formula III: [ka] During the ceremony, M is Pd or Pt; rings C and D are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; M 1 and M 2 are each independently C or N; A 1 ~A 3 are each independently C or N; K 1 and K 2 are each independently selected from the group consisting of a direct bond, O, and S; L 1 ~L 3 are each independently selected from the group consisting of a direct bond, O, S, CR'R'', SiR'R'', BR', and NR'; R' and R'' are each independently selected from the group consisting of hydrogen or the generic substituents described herein; m, n, and o are each independently 0 or 1; m+n+o=2 or 3; R C and R D are R in formula I, A the remaining variables are the same as previously defined; and any two substituents can be joined or fused together to form a ring.

[0079] With respect to Formula III, in some embodiments, L 2 can be a direct bond or NR'. In some embodiments, L 3can be O, CNR'. In some embodiments, m can be 0. In some embodiments, ring C can be a 5-membered aromatic ring. In some embodiments, ring D can be a 6-membered aromatic ring. In some embodiments, M 1 can be N, M 2 can be C. In some embodiments, M 1 can be C, M 2 can be N. In some embodiments, A 1 , A 2 , and A 3 Each of A can be C. In some embodiments, A 1 can be N, A 2 can be C, A 3 can be C. In some embodiments, A 1 can be C, A 2 can be C, A 3 can be C. In some embodiments, K 1 and K 2 can be a direct bond. In some embodiments, M can be Pt.

[0080] In some embodiments of the compound having formula III, the compound is selected from the group consisting of (V i )Pt(W j wherein i is an integer from 1 to 28, j is an integer from 1 to 57, and V i has the following structure: [ka] [ka] [ka] In the formula, W j has the following structure: [ka] [ka] [ka] wherein X is B, Al, Ga, or In; R E , R F , R G , R H , R I , and R J is R in formula I A has the same definition as R 5 ~R 28 is R in formula I 1 It has the same definition as

[0081] In some embodiments of the compound having formula III, the compound can be selected from the group consisting of: [ka] wherein all variables are as previously defined.

[0082] In some embodiments of the compound having formula III, the compound is a compound Pt(L Ax )(L Ax’ ) and the compound Pt(L Ax )(L By ), wherein L Ax is the following L Ax Ligands based on Y can be selected, and L Ax’ is the L in LA list 3 below. Ax’ The ligand may be selected from Y-based ligands, where Y is an integer from 1 to 74. [ka] [ka] [ka]

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

[0083] In some embodiments, the compound may be selected from the group consisting of: [ka] [ka] In the formula, R E is R in formula I A the remaining variables are as previously defined.

[0084] In some embodiments, the compound can be selected from the group consisting of structures set forth in Compound List 2 below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] C. OLEDs and Devices of the Present Disclosure

[0085] In another aspect, the present disclosure also provides an OLED device comprising an organic layer containing a compound disclosed in the Compounds section of this disclosure.

[0086] In some embodiments, the organic layer comprises a ligand L of formula I: A The compound may include a compound comprising: [ka] In the formula, ring A and ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; 1 ~Z 5 are each independently C or N; X is BR 1 , B.R. 1 R 2 , AlR 1 , AlR 1 R 2 , GaR 1 , GaR 1 R 2 ,InR 1 ,InR 1 R 2 , CO, SO 2 , or POR 1 and Y is NR 3 , N.R. 3 R 4 , P.R. 3 , O, S, SO, SO 2 , C.R. 3 R 4 , SiR 3 R 4 , P.R. 3 R 4 , or GeR 3 R 4 ;R A and R B each represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R A , R B , R 1 , R 2 , R 3 , and R 4each is independently hydrogen or a general substituent as defined herein; any two substituents can be bonded or fused together to form a ring, and said ligand L A is coordinated to the metal M by two labeled wavy lines; the ligand L A can be combined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands.

[0087] In some embodiments, the organic layer can be an emissive layer and the compounds described herein can be emissive or non-emissive dopants.

[0088] In some embodiments, the organic layer can further include a host, the host including a triphenylene, including a benzo-fused thiophene or a benzo-fused furan, and any substituents in the host can be independently selected from the group consisting of C n H 2n+1 , O.C. n H 2n+1 , OAr 1 , N(C n H 2n+1 ) 2 , N(Ar 1 )(Ar 2 ), CH=CH-C n H 2n+1 , C≡CC n H 2n+1 , Ar 1 , Ar 1 -Ar 2 , C n H 2n -Ar 1 or unsubstituted, n is 1 to 10, and Ar 1 and Ar 2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

[0089] In some embodiments, the organic layer can further include a host, the host comprising at least one chemical moiety selected from the group consisting of naphthalene, fluorene, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-naphthalene, aza-fluorene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene).

[0090] In some embodiments, the host may be selected from the group of hosts selected from the group consisting of: [ka] [ka] [ka]

[0091] In some embodiments, the organic layer can further comprise a host, wherein the host comprises a metal complex.

[0092] In some embodiments, the compound described herein can be a sensitizer, and the device can further include an acceptor, and the acceptor can be selected from a fluorescent emitter, a delayed fluorescent emitter, and combinations thereof.

[0093] In yet another embodiment, the OLED of the present disclosure can also include a light-emitting region that includes a compound disclosed in the Compounds section of this disclosure.

[0094] In some embodiments, the emissive region comprises a ligand L of formula I: AThe compound may include a compound comprising: [ka] In the formula, ring A and ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; 1 ~Z 5 are each independently C or N; X is BR 1 , B.R. 1 R 2 , AlR 1 , AlR 1 R 2 , GaR 1 , GaR 1 R 2 ,InR 1 ,InR 1 R 2 , CO, SO 2 , or POR 1 and Y is NR 3 , N.R. 3 R 4 , P.R. 3 , O, S, SO, SO 2 , C.R. 3 R 4 , SiR 3 R 4 , P.R. 3 R 4 , or GeR 3 R 4 ;R A and R B each represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R A , R B , R 1 , R 2 , R 3 , and R 4 each is independently hydrogen or a general substituent as defined herein; any two substituents can be bonded or fused together to form a ring, and said ligand L A is coordinated to the metal M by two labeled wavy lines; the ligand L A can be combined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands.

[0095] In yet another aspect, the present disclosure also provides a consumer product comprising an OLED having an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound disclosed in the Compounds section of the present disclosure.

[0096] In some embodiments, the consumer product is an OLED having an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a first ligand L of Formula I: A The present invention includes an OLED that can include a compound comprising: [ka] In the formula, ring A and ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; 1 ~Z 5 are each independently C or N; X is BR 1 , B.R. 1 R 2 , AlR 1 , AlR 1 R 2 , GaR 1 , GaR 1 R 2 ,InR 1 ,InR 1 R 2 , CO, SO 2 , or POR 1 and Y is NR 3 , N.R. 3 R 4 , P.R. 3 , O, S, SO, SO 2 , C.R. 3 R 4 , SiR 3 R 4 , P.R. 3 R 4 , or GeR 3 R 4 ;R A and R B each represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R A , RB , R 1 , R 2 , R 3 , and R 4 each is independently hydrogen or a general substituent as defined herein; any two substituents can be bonded or fused together to form a ring, and said ligand L A is coordinated to the metal M by two labeled wavy lines; the ligand L A can be combined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands.

[0097] In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for indoor or outdoor illumination and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a mobile phone, a tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall including multiple displays aligned together, a theater or stadium screen, a light therapy device, and a sign.

[0098] In general, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons migrate to the oppositely charged electrode, respectively. When an electron and hole localize on the same molecule, an "exciton" is formed, which is a localized electron-hole pair having an excited energy state. Light is emitted via a photoemissive mechanism when the exciton relaxes. In some cases, the exciton may be localized on an excimer or exciplex. Non-radiative mechanisms such as thermal relaxation may also occur, but are generally considered undesirable.

[0099] Some OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated by reference in their entireties.

[0100] Early OLEDs used emissive molecules that emitted light from their singlet state ("fluorescence"), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs on a time frame of less than 10 nanoseconds.

[0101] More recently, OLEDs have been demonstrated that have emissive materials that emit light from triplet states ("phosphorescence"). Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, Vol. 395, pp. 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, No. 3, pp. 4-6 (1999) ("Baldo-II"), which are incorporated by reference in their entireties. Phosphorescence is described in further detail in U.S. Pat. No. 7,279,704, columns 5-6, which are incorporated by reference.

[0102] FIG. 1 shows an organic light-emitting device 100. The figures are not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole-injection layer 120, a hole-transport layer 125, an electron-blocking layer 130, an emissive layer 135, a hole-blocking layer 140, an electron-transport layer 145, an electron-injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in US Pat. No. 7,279,704, columns 6-10, which are incorporated by reference.

[0103] Further examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is a 50:1 molar ratio of m-MTDATA to F, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. 4-TCNQ doped. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which are incorporated by reference in their entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes with 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 by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0104] FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers described, in order. Because the most common OLED configuration has the cathode disposed above the anode, and device 200 has cathode 215 disposed below anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides an example of how some layers may be omitted from the structure of device 100.

[0105] The simple layer structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that the embodiments of the present disclosure may be used in conjunction with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. A functional OLED may be achieved by combining the various layers described in various ways, or layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. While many of the examples provided herein describe the various layers as including a single material, it is understood that combinations of materials, such as mixtures of hosts and dopants, or more generally mixtures, may be used. Layers may also have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include a single layer, or may further include multiple layers of different organic materials, such as those described with respect to Figures 1 and 2.

[0106] Structures and materials not specifically described may be used, such as OLEDs (PLEDs) composed of polymeric materials such as those disclosed in U.S. Patent No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As a further example, OLEDs 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 by reference in its entirety. OLED structures may deviate from the simple layered structures illustrated in Figures 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as the mesa structures described in U.S. Patent No. 6,091,195 to Forrest et al. and / or the recessed structures described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0107] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal evaporation, such as those described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety, inkjet, organic vapor phase deposition (OVPD), such as those described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and organic vapor jet printing (OVJP), such as those 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 a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include patterning associated with some of the deposition methods such as deposition through masks, cold welding, and inkjet and organic vapor jet printing (OVJP), such as those described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety. Other methods may be used. The material to be deposited may be modified to be compatible with the particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents with 20 or more carbons may be used, with 3-20 carbons being a preferred range. Materials with asymmetric structures may have better solution processability than those with symmetric structures, as asymmetric materials may be less prone to recrystallization. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0108] Devices fabricated according to embodiments of the present disclosure may further include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment, including moisture, vapors and / or gases, etc. The barrier layer may be deposited on, under or next to the substrate, the electrodes, or on any other portion 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 or organic compounds or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials, as described in U.S. Pat. No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entireties. To be considered a "mixture", the polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymeric to non-polymeric materials can be in the range of 95:5 to 5:95. The polymeric and non-polymeric materials can be made from the same precursor materials. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

[0109] Devices made according to embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electrical products or intermediate components. Such electrical 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. Such electronic component modules can optionally include driving electronics and / or power sources. Devices made according to embodiments of the present disclosure can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Disclosed are consumer products that include OLEDs that include compounds of the present disclosure in the organic layer of the OLED. Such consumer products include any type of product that includes one or more light sources and / or one or more visual displays of some kind. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor illumination and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays aligned together, theater or stadium screens, phototherapy devices, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices made according to the present disclosure. Many of the devices are intended for use within a temperature range that is comfortable for humans, such as 18 degrees Celsius to 30 degrees Celsius, and more preferably room temperature (20-25°C), but may also be used outside this temperature range, for example, between -40 degrees Celsius and +80 degrees Celsius.

[0110] Further details regarding OLEDs and the above definitions can be found in US Pat. No. 7,279,704, which is incorporated by reference in its entirety.

[0111] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. More generally, organic devices such as organic transistors may use the materials and structures.

[0112] In some embodiments, the OLED has one or more properties 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 comprises a layer comprising carbon nanotubes.

[0113] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an RGB pixel array or a white and color filter pixel array. 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 having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having 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.

[0114] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can generate luminescence via phosphorescence, fluorescence, thermally activated delayed fluorescence, or TADF (also called E-type delayed fluorescence; see, for example, U.S. Application No. 15 / 700,352, which is incorporated by reference in its entirety), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emissive dopant can be a racemic mixture or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from the others). If there is more than one ligand that coordinates to the metal, in some embodiments, the ligands can all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, all of the ligands can be different from each other. This is true even in embodiments where a ligand coordinated to a metal can be bonded to other ligands coordinated to the metal to form tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, when the coordinating ligands are bonded to one another, in some embodiments, all of the ligands can be the same, while in some other embodiments, at least one of the bonded ligands can be different from the other ligands.

[0115] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, where one or more layers in the OLED include an acceptor in the form of one or more fluorescent and / or delayed fluorescent emitters. In some embodiments, the compound can be used as one component of an exciplex used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor, which emits energy or further transfers energy to a final emitter. The acceptor concentration can range from 0.001% to 100%. The acceptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can come from any or all of the sensitizer, the acceptor, and the final emitter.

[0116] In accordance with other aspects, compositions including the compounds described herein are also disclosed.

[0117] The OLEDs disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer, and in some embodiments, the compound can be an emissive dopant, and in other embodiments, the compound can be a non-emissive dopant.

[0118] In yet another aspect of the present disclosure, a composition is described that includes the novel compounds disclosed herein. The composition may also include one or more components selected from the group consisting of a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material disclosed herein.

[0119] The present disclosure encompasses any chemical structure that includes the novel compounds of the present disclosure, or monovalent or polyvalent variants thereof. In other words, the compounds of the present invention, or monovalent or polyvalent variants thereof, can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also known as supermolecules). As used herein, a "monovalent variant of a compound" refers to a moiety that is identical to the compound, except that one hydrogen has been removed and replaced with a bond to the remainder of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to a moiety that is identical to the compound, except that more than one hydrogen has been removed and replaced with a bond to the remainder of the chemical structure. In the example of a supramolecule, the compounds of the present invention can also be incorporated into the supramolecular complex without a covalent bond. D. Combinations of Compounds of the Present Disclosure with Other Materials

[0120] The materials described herein as useful for a particular layer in an organic light-emitting device can 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 in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present.The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that may be useful in combination. a) Conductive dopants:

[0121] The charge transport layer is doped with a conductive dopant to significantly change the density of charge carriers and therefore its conductivity. The conductivity can be increased by creating charge carriers in the matrix material or, 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.

[0122] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with references that disclose these materials. EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012 [ka] [ka] b) HIL / HTL:

[0123] The hole injection / transport material used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injection / transport material. Examples of materials include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorocarbons; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembly monomers derived from compounds such as phosphonic acid and silane derivatives; MoO xp-type semiconducting organic compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes, and crosslinkable compounds.

[0124] Examples of aromatic amine derivatives used in the HIL or HTL include, but are not limited to, the following general structure: [ka]

[0125] Ar 1 From Ar 9each of the above represents a group consisting of aromatic hydrocarbon ring compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazole, and aromatic heterocyclic compounds such as sazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and aromatic hydrocarbon ring groups and aromatic heterocyclic groups, which may be of the same or different types and which 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 Ar can be unsubstituted or substituted with substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0126] In one embodiment, Ar 1 From Ar9 teeth, [ka] (wherein k is an integer from 1 to 20; X 101 From X 108 is C (including CH) or N; Z 101 is NAr 1 , O, or S; Ar 1 has the same groups as defined above.

[0127] Examples of metal complexes used in the HIL or HTL include, but are not limited to, those of the general formula: [ka] where Met is a metal that may have an atomic weight greater than 40; 101 -Y 102 ) is a bidentate ligand, and Y 101 and Y 102 is independently selected from C, N, O, P, and S; L 101 is an ancillary ligand; k' is an integer value from 1 to the maximum number of ligands that may be bound to the metal; and k'+k'' is the maximum number of ligands that may be bound to the metal.

[0128] In one embodiment, (Y 101 -Y 102 In another embodiment, (Y 101 -Y 102 In another embodiment, Met is selected from Ir, Pt, Os, and Zn. In a further embodiment, the metal complex is + For the / Fc couple, it has a minimum oxidation potential of less than about 0.6 V in solution.

[0129] Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with references that disclose these materials. CN102702075、DE102012005215、EP01624500、EP01698613、EP01806334、EP01930964、EP01972613、EP01997799、EP02011790、EP02055700、EP02055701、EP1725079、EP2085382、EP2660300、EP650955、JP07-073529、JP2005112765、JP2007091719、JP2008021687、JP2014-009196、KR20110088898、KR20130077473、TW201139402、US06517957、US20020158242、US20030162053、US20050123751、US20060182993、US20060240279、US20070145888、US20070181874、US20070278938、US20080014464、US20080091025、US20080106190、US20080124572、US20080145707、US20080220265、US20080233434、US20080303417、US2008107919、US20090115320、US20090167161、US2009066235、US2011007385、US20110163302、US2011240968、US2011278551、US2012205642、US2013241401、US20140117329、US2014183517、US5061569、US5639914、WO05075451、WO07125714、WO08023550、WO08023759、WO2009145016、WO2010061824、WO2011075644、WO2012177006、WO2013018530、WO2013039073、WO2013087142、WO2013118812、WO2013120577、WO2013157367、WO2013175747、WO2014002873、WO2014015935、WO2014015937、WO2014030872、WO2014030921、WO2014034791、WO2014104514、WO2014157018 [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] c) EBL:

[0130] Electron blocking layers (EBLs) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Blocking layers can also be used to confine emission to desired regions of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group used as one of the hosts described below. d) Host:

[0131] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. The host material is not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant as long as the triplet criteria are met.

[0132] Examples of metal complexes used as host materials preferably have the general formula: [ka] where Met is a metal; 103 -Y 104 ) is a bidentate ligand, and Y 103 and Y 104 is 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 may be bound to the metal; and k'+k'' is the maximum number of ligands that may be bound to the metal.

[0133] In one embodiment, the metal complex is a complex: [ka] where (ON) is a bidentate ligand with the metal coordinated to atoms O and N.

[0134] In another embodiment, Met is selected from Ir and Pt. 103 -Y 104 ) is a carbene ligand.

[0135] In one embodiment, the host compound is selected from the group consisting of aromatic hydrocarbon ring compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazoline, and aromatic heterocyclic compounds such as benzofuropyridine, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and aromatic hydrocarbon ring groups and aromatic heterocyclic groups, which are the same or different groups and which have 2 to 10 cyclic structural units 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 cyclic group. Each option within each group can be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0136] In one embodiment, the host compound contains at least one of the following groups in the molecule: [ka] [ka] In the formula, R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, has the same definition as that of Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X 101 ~X 108 is independently selected from C (including CH) or N. 101 and Z 102 is independently, NR 101 , O, or S.

[0137] Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with references that disclose these materials. EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564 , TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US2 0090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012 126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO200706375 4. WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO20100 56066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO 2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803

change

change

change

change

[0138] One or more additional emitter dopants can be used with the compounds of the present disclosure.The examples of the additional emitter dopants are not particularly limited, and any compound can be used as long as the compound is typically used as an emitter material.Examples of suitable emitter materials include, but are not limited to, compounds that can generate luminescence via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e. TADF (also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0139] Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with references that disclose these materials. CN103694277、CN1696137、EB01238981、EP01239526、EP01961743、EP1239526、EP1244155、EP1642951、EP1647554、EP1841834、EP1841834B、EP2062907、EP2730583、JP2012074444、JP2013110263、JP4478555、KR1020090133652、KR20120032054、KR20130043460、TW201332980、US06699599、US06916554、US20010019782、US20020034656、US20030068526、US20030072964、US20030138657、US20050123788、US20050244673、US2005123791、US2005260449、US20060008670、US20060065890、US20060127696、US20060134459、US20060134462、US20060202194、US20060251923、US20070034863、US20070087321、US20070103060、US20070111026、US20070190359、US20070231600、US2007034863、US2007104979、US2007104980、US2007138437、US2007224450、US2007278936、US20080020237、US20080233410、US20080261076、US20080297033、US200805851、US2008161567、US2008210930、US20090039776、US20090108737、US20090115322、US20090179555、US2009085476、US2009104472、US20100090591、US20100148663、US20100244004、US20100295032、US2010102716、US2010105902、US2010244004、US2010270916、US20110057559、US20110108822、US20110204333、US2011215710、US2011227049、US2011285275、US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US 2014103305, US6303238, US6413656, US6653654, US6670645, US6687266, US6835469, US6921915, US7279704, US73 32232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586 , US8871361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO200201 5645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842 , WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO20 11044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO201317 4471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450,

change

change

change

change

[0140] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the HBL interface.

[0141] In one embodiment, the compounds used in the HBL contain the same molecules or the same functional groups as those used in the hosts described above.

[0142] In another embodiment, the compound used in the HBL comprises at least one of the following groups in the molecule: [ka] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3. g)ETL:

[0143] The electron transport layer (ETL) may include a material 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 typically used to transport electrons.

[0144] In one embodiment, the compound used in the ETL contains at least one of the following groups in the molecule: [ka] In the formula, R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, has the same definition as that of Ar mentioned above. 1 From Ar 3 has the same definition as that of Ar mentioned above. k is an integer from 1 to 20. X 101 From X 108 is selected from C (including CH) or N.

[0145] In another embodiment, the metal complex used in the ETL comprises, but is not limited to, the following general formula: [ka] In the formula, (ON) or (NN) is a bidentate ligand having a metal coordinated to the atoms O, N or N, N; 101 is another ligand; and k' is an integer value between 1 and the maximum number of ligands that can be bound to the metal.

[0146] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with references that disclose these materials. CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2 005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, U S20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US20 11210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO20 09148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, W O2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535 [ka] [ka] [ka] h) Charge Generation Layer (CGL)

[0147] In tandem or stacked OLEDs, the CGL plays an important role in performance and consists of n-doped and p-doped layers for the injection of electrons and holes, respectively. The electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively, after which the bipolar current gradually reaches a steady state. Typical CGL materials contain n-type and p-type conductive dopants used in the transport layers.

[0148] In any of the above-mentioned compounds used in each layer of an OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any of the specifically mentioned substituents, such as but not limited to methyl, phenyl, pyridyl, etc., can be their non-deuterated, partially deuterated, and fully deuterated versions. Similarly, the classes of substituents, such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc., can be their non-deuterated, partially deuterated, and fully deuterated versions. E. Experimental Section of the Disclosure a) Preparation of example compounds

[0149] Potassium (2,6-diisopropylphenyl)trifluoroborate [ka] Potassium fluoride (18.0 g, 310 mmol) in water (30 mL) was added to a stirred solution of (2,6-diisopropylphenyl)boronic acid (15 g, 73 mmol) in acetonitrile (300 mL) at RT. A warm solution of L-(+)-tartaric acid (22.5 g, 150 mmol) in THF (165 mL) was added and the mixture was stirred at 45 °C overnight. The reaction mixture was filtered and the filtrate was concentrated. The resulting solid was suspended in 1:1 isohexane / MTBE (200 mL), stirred at RT for 1.5 h, and filtered (additional 1:1 isohexane:MTBE (3 x 40 mL) was required to complete the transfer to the filter). The solid was dried in a vacuum desiccator to give potassium (2,6-diisopropylphenyl)trifluoroborate (10.5 g, 38.2 mmol, 53% yield, >98% purity) as a white solid.

[0150] [1,1':3',1''-terphenyl]-2'-ylboronic acid [ka] To a solution of 2'-iodo-1,1':3',1''-terphenyl (6.85 g, 19.2 mmol) in CPME (70 mL) at RT was added nBuLi (2 M in hexanes, 10 mL, 20 mmol) over 10 min. The reaction mixture was stirred at RT for 2 h and then cooled to -70°C. Triisopropylborate (7.0 mL, 31 mmol) was added over 10 min and the reaction was stirred at RT overnight. The reaction mixture was diluted with DCM (200 mL) and diluted with 10% K 2 HPO 4 (aq) (2 × 100 mL) and brine (100 mL). The combined aqueous layers were back-extracted with DCM (2 × 100 mL) and the combined organic layers were extracted with MgSO 4The mixture was dried over ice, filtered and concentrated. The residue was dissolved in DCM (50 mL) and acetic acid (3.0 mL, 52 mmol) was added with vigorous stirring followed by water (1.5 mL, 83 mmol). The resulting mixture was left under stirring for 2 h and then concentrated in vacuo. The residue was suspended in heptane (15 mL) and the solid was collected by filtration and the filter cake was rinsed with heptane (5 x 5 mL) to give [1,1':3',1''-terphenyl]-2'-ylboronic acid (3.21 g, 11.4 mmol, 59% yield, >98% purity) as a white solid.

[0151] 3,5-Diisopropyl-[1,1'-biphenyl]-4-amine [ka] A nitrogen purged flask containing 4-bromo-2,6-diisopropylaniline (10 g, 39 mmol), phenylboronic acid (5.5 g, 45 mmol), and SPhos-Pd(crotyl)Cl [CAS: 1798781-99-3] (500 mg, 0.823 mmol) was charged with acetonitrile (100 mL) and K 2 CO 3 (aq) (1.5 M, 80 mL, 120 mmol). The reaction mixture was stirred vigorously under nitrogen at 75° C. for 16 h. The reaction was cooled and filtered. After layer separation, the organics were washed with 20% w / w NaCl(aq) (100 mL), preadsorbed onto silica gel (30 g) and purified by column chromatography to give 3,5-diisopropyl-[1,1′-biphenyl]-4-amine (5.5 g, 21 mmol, 53% yield, 95% purity) as a thick colorless oil.

[0152] 4-Iodo-3,5-diisopropyl-1,1'-biphenyl [ka] Tosylic acid monohydrate (pTSA, 7.5 g, 39 mmol) was added to a beaker. tTo a stirred solution of 3,5-diisopropyl-[1,1'-biphenyl]-4-amine (3.4 g, 13 mmol) in BuOH (50 mL) was added. A thick, non-mobile precipitate formed. Water (5 mL) and t BuOH (10 mL) was added. A solution of sodium nitrite (2.0 g, 29 mmol) and KI (6.0 g, 36 mmol) in water (20 mL) was added dropwise (gas evolution). The mixture was hand mixed with a spatula until stirring resumed, after which vigorous stirring was continued for 90 min. The reaction mixture was diluted with saturated Na 2 S 2 O 3 (60 mL) and EtOAc (100 mL), the organics were separated, dried (MgSO4), filtered and concentrated. The crude product was pre-adsorbed onto silica gel (10 g) and purified by column chromatography to give 4-iodo-3,5-diisopropyl-1,1'-biphenyl (3.7 g, 9.9 mmol, 73% yield, 97% purity) as a colorless oil which crystallized on standing.

[0153] (3,5-Diisopropyl-[1,1'-biphenyl]-4-yl)boronic acid [ka] n BuLi (2M in hexanes, 6.0 mL, 12 mmol) was added dropwise to a solution of 4-iodo-3,5-diisopropyl-1,1'-biphenyl (4.5 g, 12 mmol) in dry CPME (50 mL) at RT under nitrogen. A slight exotherm from 20°C to 25°C was noted and a thick tan precipitate formed. The reaction was left stirring under nitrogen for 2 h, cooled to -70°C and trimethylborate (1.8 mL, 16 mmol) was added dropwise. The reaction was allowed to warm to RT overnight and quenched with 1M HCl(aq) (20 mL). The organic layer was separated and the aqueous layer was extracted with TBME (20 mL). The combined organic layers were washed with MgSO 4The mixture was dried over ice, filtered and concentrated to give a thick oil which crystallized on standing. The solid was triturated with hexanes and filtered to give a tan solid. This solid was suspended in 1M HCl(aq) (20 mL) and MeCN (20 mL), stirred vigorously at 75 °C for 2 h and cooled to RT. The mixture was extracted with TBME (20 mL) and MgSO 4 The residue was dried over 100 ml, filtered, and preadsorbed onto silica gel (5 g). Purification by column chromatography afforded (3,5-diisopropyl-[1,1'-biphenyl]-4-yl)boronic acid (1.9 g, 6.7 mmol, 55% yield, >98% purity) as a colorless solid.

[0154] Dimethyl (2,4,6-tri-tert-butylphenyl)boronate [ka] 2-Bromo-1,3,5-tri-tert-butylbenzene (2 g, 6.15 mmol) was dissolved in N 2 It was dissolved in THF (25 mL) under atmospheric pressure and cooled to -78°C. n-Butyllithium (2.5 ml, 6.25 mmol) was added and the resulting solution was stirred at -78°C for 1 h. Trimethylborate (.7 ml, 6.28 mmol) was added and the reaction was then heated to 50°C for 3 days. The reaction was quenched with 1M aqueous HCl, then transferred to a separatory funnel and diluted with DCM. After layer separation, the aqueous layer was extracted with DCM. The combined organics were washed with brine, dried (Na 2 SO 4 ), filtered, concentrated, and purified by column chromatography to give 0.88 g (45%) of dimethyl (2,4,6-tri-tert-butylphenyl)boronate as a colorless oil that slowly crystallized to a white solid.

[0155] 2-(2-fluorophenyl)-1H-imidazole [ka] Ammonium acetate (105 g, 1362 mmol) was added to a solution of 2-fluorobenzaldehyde (28 ml, 266 mmol) and glyoxal (40% aq., 63 ml, 549 mmol) in water (250 ml) and methanol (250 ml) and the mixture was stirred at RT for 16 h. The MeOH was removed on a rotovap and the aqueous layer was extracted with 3×150 mL EtOAc. The organics were combined and washed with 3×100 mL saturated NaHCO 3 After washing with aqueous solution, Na 2 SO 4 The mixture was dried over ice. Solvent removal gave a brown oil which was purified by column chromatography to give a crystallized product which was washed with ether / heptane to give 13.78 g (32%) of an off-white solid.

[0156] 2-(2-fluoro-4-methylphenyl)-1H-imidazole [ka] 2-Fluoro-4-methylbenzaldehyde (26.3 ml, 181 mmol) was dissolved in 400 mL of MeOH in a 2 L RBF, followed by the addition of 200 mL of a 40% aqueous solution of glyoxal (200 ml, 1744 mmol). Ammonium hydroxide (30% hydroxide, 200 ml, 1541 mmol) was then added in portions over ∼15 min, and the yellow solution was flushed with N 2 The mixture was stirred under reduced pressure for 24 hours. The grey solid was collected by suction filtration and washed with MeOH. The solid was then slurried in EtOAc (3×50 mL) and filtered. The combined filtrate was taken to dryness to give a brown solid which was purified by sublimation to give 11.01 g (35%) of a beige crystalline solid.

[0157] 2-(2-fluorophenyl)-4,5,6,7-tetrahydro-1H-benzo[d]imidazole [ka] Cyclohexane-1,2-dione (5.00 g, 44.6 mmol) was placed in a 500 mL 2-neck RBF, followed by the addition of 150 mL of iPrOH via syringe to give a pale yellow solution 2-fluorobenzaldehyde (11.75 ml, 111 mmol), followed by the addition of solid ammonium acetate (34.4 g, 446 mmol). The heterogeneous mixture was heated to reflux in a sand bath for 24 h, during which time it turned orange, then red, and finally red and completely homogeneous. After cooling to RT, the iPrOH was removed by rotary evaporation to give a bright red liquid, which was taken up in DCM (300 mL) and saturated NaHCO 3 After washing with aqueous solution and water, Na 2 SO 4 The mixture was dried over ice. Solvent removal gave a light red foam which was purified by column chromatography to give an orange solid which upon trituration with heptane gave 3.40 g (35%) of the desired compound as a yellow semi-crystalline solid.

[0158] 2-Fluoro-3-(1H-imidazol-2-yl)pyridine [ka] To a 1 L RBF was added a 40% aqueous solution of glyoxal (100 ml, 872 mmol), followed by 200 mL of MeOH. To the colorless solution was added 2-fluoronicotinaldehyde (8.00 ml, 80 mmol), neat, to give a pale yellow solution. Ammonium hydroxide (30% in water, 100 ml, 770 mmol) solution was added in several portions, with small amounts of ice added between each portion over ~10 min to prevent MeOH reflux. 2 The mixture was stirred under reduced pressure for 16 h. 300 mL of water was added and the mixture was extracted with 3×150 mL of EtOAc. The organics were combined and washed with 1×100 mL of brine and added Na 2 SO 4 Drying on ice and evaporation gave a semi-crystalline solid which was purified by column chromatography to give a colourless crystalline solid (4.52 g, 35%).

[0159] 2-(2-Bromophenyl)-4-phenyl-1H-imidazole [ka] To a suspension of 2-bromobenzimidamide hydrochloride (40.4 g, 168 mmol) in THF (300 mL) and water (75 mL) was added sodium bicarbonate (30 g, 350 mmol) in portions over 5 min. The reaction mixture was heated to 70 °C and stirred for 50 min (gas evolution ceased). A solution of 2-bromo-1-phenylethan-1-one (33.5 g, 168 mmol) in THF (195 mL) was added dropwise over 15 min while maintaining reflux. The reaction mixture was then stirred overnight at 70 °C, cooled to RT and concentrated in vacuo to give an orange oil. The crude product was diluted with DCM (1 L) and water (300 mL) and the aqueous layer was extracted with DCM (300 mL). The combined organic layers were washed with MgSO 4 The mixture was dried over ice, filtered and pre-adsorbed onto silica gel. The material was purified by column chromatography then suspended in isohexane (300 mL), heated to 55° C. for 5 h, cooled to RT and stirred overnight. The mixture was concentrated in vacuo to give 2-(2-bromophenyl)-4-phenyl-1H-imidazole (27.1 g, 53% yield, >98% purity) as an orange solid.

[0160] 2-(2-Bromophenyl)-4,5-diphenyl-1H-imidazole [ka] Benzil (13.6 g, 64.9 mmol), ammonium acetate (41.7 g, 540 mmol) and 2-bromobenzaldehyde (6.3 mL, 54 mmol) were suspended in acetic acid (200 mL) and the mixture was stirred at 90 °C for 24 h. The reaction mixture was cooled and the pH was adjusted to ~6 with 2 M NaOH (aq) (ca. 1.5 L). The precipitated solid was collected by filtration and the filter cake was rinsed with water (500 mL) and toluene (500 mL). The resulting solid was suspended in DCM (250 mL), stirred at RT for 2 h, collected by filtration and dried in a vacuum desiccator to give 2-(2-bromophenyl)-4,5-diphenyl-1H-imidazole (16.6 g, 43.9 mmol, 81% yield, >98% purity) as an off-white solid.

[0161] 2-(1H-imidazol-2-yl)phenol [ka] Ammonium acetate (67 g, 869 mmol) was added to a solution of salicylaldehyde (15.5 ml, 145 mmol) and glyoxal (25 ml, 218 mmol) in water (200 ml):methanol (200 ml) and the mixture was stirred at room temperature for 2 h. The reaction mixture was concentrated to remove MeOH and then transferred to a separatory funnel. Extraction with EtOAc was followed by washing the combined organics with NaHCO 3 The organics were dried (Na 2 SO 4 ), filtered, concentrated, and then purified by column chromatography to give 8.91 g (38% yield) of 2-(1H-imidazol-2-yl)phenol as an off-white crystalline solid.

[0162] 2-(4,5-diphenyl-1H-imidazol-2-yl) [ka] Benzil (4 g, 19.03 mmol) and ammonium acetate (16 g, 208 mmol) were combined in acetic acid (30 ml) and heated to 120° C. under N2 atmosphere until all solids were dissolved. After adding 2-hydroxybenzaldehyde (10 ml, 94 mmol), the reaction was refluxed for 4 h. After cooling to rt, the reaction mixture was poured into 80 mL of water. The resulting solution was neutralized with ammonium hydroxide solution, then transferred to a separatory funnel and diluted with EtOAc. After layer separation, the aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine, dried (Na 2 SO 4 ), filtration, concentration, and purification by column chromatography gave 2.38 g (40% yield) of 2-(4,5-diphenyl-1H-imidazol-2-yl)phenol as an off-white solid.

[0163] 2-(1H-imidazol-2-yl)-N-methylaniline [ka] A nitrogen purged flask containing 2-(2-bromophenyl)-1H-imidazole (10 g, 45 mmol), copper(I) iodide (0.40 g, 2.1 mmol), and freshly ground potassium phosphate (30 g, 140 mmol) was charged with DMSO (150 mL) and methanamine (33% wt in EtOH, 100 mL, 800 mmol). The reaction mixture was stirred at 45° C. for 1 h and then filtered. The filtrate was slowly poured into water (1 L) and stirred for 1 h. The resulting solid was collected by filtration and dried (6 g). The filtrate was extracted with TBME (3×500 mL) and the combined organic layers were concentrated to give a yellow gum (1.8 g, fraction 1). The solid was suspended in THF (250 mL) and filtered. The filtrate was evaporated to give a yellow gum that crystallized on standing (fraction 2). Fractions 1 and 2 were combined in THF, preadsorbed onto silica gel (30 g), and purified by column chromatography to give 2-(1H-imidazol-2-yl)-N-methylaniline (5.4 g, 31 mmol, 70% yield, >98% purity) as a colorless crystalline solid.

[0164] 2-(1H-imidazol-2-yl)-N-isopropylaniline [ka] A 250 mL RBF was charged with 2-(2-fluorophenyl)-1H-imidazole (1.16 g, 7.15 mmol) followed by 40 mL of diglyme to give a colorless solution. Isopropylamine (1.60 ml, 19.54 mmol) was added neat via syringe and the solution was cooled to 0° C. before isopropylmagnesium chloride (2.0 M, 12 ml, 24.00 mmol) was added dropwise over ∼15 min. The mixture was heated to 150° C. for 3 h, cooled to RT and washed with saturated NH 4 The mixture was quenched with aqueous Cl and extracted with 3×20 mL of DCM. The organics were combined and washed with Na 2 SO 4 The mixture was dried over ice. The solvent was removed to give a brown oil which solidified on cooling. The compound was purified by column chromatography and isolated as a colorless solid, 1.29 g (90%).

[0165] 2-(1H-imidazol-2-yl)-5-methyl-N-phenylaniline [ka] 2-(2-Fluoro-4-methylphenyl)-1H-imidazole (3.00 g, 17.03 mmol) was placed in a 500 mL oven-dried RBF with N 2 After the flask was cooled to 0° C. in an ice / water bath, isopropylmagnesium chloride (2.0 M solution in THF, 26.0 ml, 52.0 mmol) was added via syringe. The flask was then fitted with a bump trap and heated to 150° C. for 3 h. The mixture was cooled to RT and saturated NH 4 The mixture was quenched with aqueous Cl. All volatiles were removed with Kughelrhor. The solid was then extracted with EtOAc / saturated NaHCO 3The organics were combined and diluted with Na 2 SO 4 Drying on ice and concentration gave a brown solid which was purified by column chromatography to give 2.70 g (64%) of an off-white solid.

[0166] N-Methyl-2-(4,5,6,7-tetrahydro-1H-benzo[d]imidazol-2-yl)aniline [ka] 2-(2-Fluorophenyl)-4,5,6,7-tetrahydro-1H-benzo[d]imidazole (3.123 g, 14.44 mmol) was dissolved in 60 mL of diglyme and cooled to 0° C. in an ice / water bath. Methylamine (2.0 M in THF, 18.00 ml, 36.0 mmol) was added via syringe followed by isopropylmagnesium chloride (2.0 M solution in THF, 21.0 ml, 42.0 mmol) dropwise over approximately 2 min. The mixture was heated to 125° C. (sand bath) for 6 h and cooled to RT. ∼20 mL of water was added and all volatiles were removed directly in a Kugelrhor to give a yellow / brown solid which was dissolved in NaHCO 3 (aq) and taken up in EtOAc (100 mL). After separation of the layers, the aqueous layer was extracted with 2×100 mL of EtOAc. The organics were combined and washed with Na 2 SO 4 The mixture was dried over ice. Removal of the solvent gave a yellow solid which was purified by column chromatography to give 1.08 g (33%) of a colorless crystalline solid which was then washed with pentane.

[0167] 3-(1H-imidazol-2-yl)-N-isopropylpyridin-2-amine [ka] 2-Fluoro-3-(1H-imidazol-2-yl)pyridine (3.00 g, 18.39 mmol) was placed in a 500 mL oven-dried RBF and dissolved in 90 mL diglyme. Isopropylamine (4.60 ml, 56.2 mmol) was added via syringe and the colorless solution was cooled to 0° C. in an ice / water bath. Isopropylmagnesium chloride in THF (2M, 23.0 ml, 46.0 mmol) was added slowly over ∼5 min and then heated to 120° C. for 16 h. A small amount of water was added and all volatiles were removed with Kugelrhor. The solid was then dissolved in EtOAc / saturated NaHCO 3 The organics were combined and diluted with Na 2 SO 4 Drying and concentration gave a brown solid which was purified by column chromatography to give 1.77 g (48%) of a colorless solid.

[0168] N-Methyl-2-(5-phenyl-1H-imidazol-2-yl)aniline [ka] To a suspension of 2-(2-bromophenyl)-5-phenyl-1H-imidazole (19.6 g, 65.5 mmol), copper(I) iodide (1.3 g, 6.8 mmol), and potassium phosphate (40.0 g, 188 mmol) in DMSO (200 mL) was added methylamine (33% wt in EtOH, 60 mL, 480 mmol). The reaction mixture was stirred at 40° C. under nitrogen for 3 h. The reaction mixture was diluted with EtOAc (600 mL) and diluted with 1:1:1 (sat. NaHCO 3 (aq)) / (saturated NH 4 Cl(aq) / brine (2 × 600 mL) and brine (200 mL), and then washed with MgSO 4 The mixture was dried over hexane, filtered and concentrated. Purification by column chromatography afforded N-methyl-2-(5-phenyl-1H-imidazol-2-yl)aniline (11.3 g, 44.4 mmol, 68% yield, >98% purity) as a yellow solid.

[0169] 2-(4,5-diphenyl-1H-imidazol-2-yl)-N-methylaniline [ka] A suspension of tripotassium phosphate (14 g, 66 mmol), 2-(2-bromophenyl)-4,5-diphenyl-1H-imidazole (8.0 g, 21 mmol), and copper(I) iodide (200 mg, 1.05 mmol) was suspended in DMSO (70 mL) under nitrogen. Methanolamine (33% in EtOH, 24 mL, 200 mmol) was added and the reaction was stirred at 60° C. overnight. The reaction was cooled to RT, diluted with water (250 mL), stirred for 30 min, and extracted with EtOAc (3×200 mL). The combined organic extracts were concentrated and the residue was triturated with EtOAc (10 mL) to give 2-(4,5-diphenyl-1H-imidazol-2-yl)-N-methylaniline (6.03 g, 17.8 mmol, 83% yield, 96% purity) as a brown solid.

[0170] 2-(5-Bromo-2-fluorophenyl)-1H-imidazole [ka] 5-Bromo-2-fluorobenzaldehyde (25 g, 123 mmol) was dissolved in MeOH (300 mL) and glyoxal solution (H 2 40% wt. in O, 100 mL, 872 mmol), followed by additional H 2 With stirring at RT, ammonium hydroxide (250 mL, 1798 mmol) was added in portions over 1 h, resulting in an exotherm and the formation of a precipitate. An additional 50 mL of H 2 O was added and the reaction mixture was then stirred overnight. The reaction was concentrated, transferred to a separatory funnel, extracted with EtOAc, and the organics were combined and washed with saturated NaHCO 3 The mixture was washed with water and brine. 2 SO 4), filtration and concentration gave a brown solid which was purified by column chromatography, triturated in DCM and collected by vacuum filtration to give 10.4 g (35% yield) of 2-(5-bromo-2-fluorophenyl)-1H-imidazole as an off-white solid.

[0171] 2-(5-Bromo-2-fluorophenyl)-1-(tetrahydro-2H-pyran-2-yl)-1H-imidazole [ka] 2-(5-Bromo-2-fluorophenyl)-1H-imidazole (7.61 g, 31.6 mmol) and 4-methylbenzenesulfonic acid hydrate (p-TSA, 0.300 g, 1.58 mmol) were combined in dioxane (30 mL) and then 3,4-dihydro-2H-pyran (15 mL, 164 mmol) was added. The mixture was cooled to 37° C. for 1 hour and then cooled to 37° C. 2 The reaction was refluxed at 100° C. under atmospheric pressure and stirred for 3 days. The reaction was cooled to room temperature and then diluted with DCM and saturated NaHCO 3 The mixture was quenched with. After separation of the layers, the aqueous layer was extracted with DCM. The combined organics were washed with brine and dried (Na 2 SO 4 ), filtered and concentrated to give a crude oil which was purified by column chromatography to give 5.57 g (54%) of 2-(5-bromo-2-fluorophenyl)-1-(tetrahydro-2H-pyran-2-yl)-1H-imidazole as a pale yellow / brown oil.

[0172] 9-(4-(tert-butyl)pyridin-2-yl)-2-(4-fluoro-3-(1-(tetrahydro-2H-pyran-2-yl)-1H-imidazol-2-yl)phenoxy)-9H-carbazole [ka] 2-(5-Bromo-2-fluorophenyl)-1-(tetrahydro-2H-pyran-2-yl)-1H-imidazole (1.07 g, 3.29 mmol), 9-(4-(tert-butyl)pyridin-2-yl-9H-carbazo-2-ol (1.04 g, 3.29 mmol), picolinic acid (0.608 g, 4.94 mmol), copper(I) iodide (0.188 g, 0.987 mmol), and potassium phosphate tribasic monohydrate (2.65 g, 11.52 mmol) were combined and dissolved in DMSO (33 mL), after which the reaction vessel was sealed with a septum, degassed by continuous evacuation, and flushed with N. 2 Refilled with N 2 The flask was placed in an oil bath at 150° C. under atmospheric pressure and the reaction was stirred for 3 days. The reaction was cooled to room temperature and the mixture was transferred to a separatory funnel containing DCM and saturated NH 4 The mixture was diluted with HCl. After separation of the layers, the aqueous layer was extracted with DCM. The combined organics were washed with water and brine. Drying (Na 2 SO 4 ), filtered and concentrated to give a crude oil which was purified by column chromatography to give 1.27 g (69% yield) of 9-(4-(tert-butyl)pyridin-2-yl)-2-(4-fluoro-3-(1-(tetrahydro-2H-pyran-2-yl)-1H-imidazol-2-yl)phenoxy)-9H-carbazole as an off-white solid.

[0173] 9-(4-(tert-butyl)pyridin-2-yl)-2-(4-fluoro-3-(1H-imidazol-2-yl)phenoxy)-9H-carbazole [ka] 4-Methylbenzenesulfonic acid hydrate (0.051 g, 0.268 mmol) was weighed into a flask containing 9-(4-(tert-butyl)pyridin-2-yl)-2-(4-fluoro-3-(1-(tetrahydro-2H-pyran-2-yl)-1H-imidazol-2-yl)phenoxy)-9H-carbazole (1.27 g, 2.265 mmol) and a stir bar. After adding methanol (40 mL), the mixture was heated to 70° C. and stirred overnight. After cooling to room temperature, the MeOH was removed in vacuo. Transferred to a separatory funnel containing DCM and diluted with saturated Na 2 CO 3 The layers were separated and the aqueous layer was extracted with DCM. The combined organics were washed with brine and dried (Na 2 SO 4 ), filtered, concentrated, and purified by column chromatography to give 1.03 g (95% yield) of 9-(4-(tert-butyl)pyridin-2-yl)-2-(4-fluoro-3-(1H-imidazol-2-yl)phenoxy)-9H-carbazole as an off-white solid.

[0174] 4-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2-(1H-imidazol-2-yl)-N-phenylaniline [ka] 9-(4-(tert-butyl)pyridin-2-yl)-2-(4-fluoro-3-(1H-imidazol-2-yl)phenoxy)-9H-carbazole (WNP2019-2-013) (.777 g, 1.630 mmol)) was dissolved in diglyme (2.5 ml). Aniline (0.38 ml, 4.16 mmol) was added and the reaction mixture was cooled to 0° C. in an ice bath. Isopropylmagnesium chloride (2.0 M in THF, 24 ml, 48.0 mmol) was then added. Warmed to rt and stirred for 30 min, then placed in a 150° C. oil bath and stirred for 4 h. Cooled to rt and then quenched with water. After solvent removal, dissolved in DCM, transferred to a separatory funnel and diluted with saturated NH 4The combined organics were washed with brine and dried (Na 2 SO 4 ), filtered, concentrated, and purified by column chromatography to give 0.718 g (80% yield) of 4-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2-(1H-imidazol-2-yl)-N-phenylaniline as a white solid.

[0175] 3-Methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline [ka] A solution of 2-bromo-3-methylaniline (530 g, 2.94 mol, 1 equiv), (2-biphenyl)dicyclohexylphosphine (41.3 g, 0.118 mmol, 0.04 equiv), and triethylamine (1.23 L, 8.83 mol, 3 equiv) in dioxane (5 L) was sparged with nitrogen for 35 minutes. Bis(acetonitrile)dichloropalladium(II) (15.3 g, 0.0589 mol, 0.02 equiv) was added and the resulting solution was sparged with nitrogen for an additional 20 minutes. The reaction mixture was cooled to 4° C. and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.854 L, 5.89 mol, 2 equiv) was added dropwise while maintaining the temperature below 10° C. The reaction temperature was slowly raised to 80° C. and stirred for 17 hours. The reaction mixture was cooled to room temperature and the resulting 3-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline was used in the next step without isolation.

[0176] 2'-Amino-4-methoxy-6'-methyl-[1,1'-biphenyl]-2-carbonitrile [ka] The reaction mixture obtained above was cooled to 0° C. Water (0.5 L) was carefully added and the solution was sparged with nitrogen for 20 minutes. 2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl (193 g, 0.471 mol, 0.16 equiv.), SPhosPdG2 (170 g, 0.236 mol, 0.08 equiv.), and potassium carbonate (407 g, 2.944 mol, 1 equiv.) were added and the reaction mixture was sparged with nitrogen for an additional 20 minutes. The reaction was refluxed at 85° C. for 20 hours, cooled to room temperature, and filtered through a pad of Celite. The filtrate was diluted with diethyl ether (5 L), washed with saturated brine (1.8 L), dried over sodium sulfate, and concentrated under reduced pressure. The resulting thick red oil was dissolved in hot toluene (4.5 L), filtered, and the filtrate was washed with water (2×2.5 L), dried over sodium sulfate, and concentrated under reduced pressure to give 2′-amino-4-methoxy-6′-methyl-[1,1′-biphenyl]-2-carbonitrile as a brown solid (850 g) which was used in the next step.

[0177] 8-Methoxy-1-methylphenanthridin-6-amine [ka] A 60% dispersion of sodium hydroxide in mineral oil (40 g, 1 mol, 0.34 equiv.) was added in portions to a solution of crude 2'-amino-4-methoxy-6'-methyl-[1,1'-biphenyl]-2-carbonitrile (850 g) in anhydrous tetrahydrofuran (4 L) at 0°C. After stirring at room temperature for 20 h, the reaction mixture was cooled to 0°C, quenched with water (50 mL), and diluted with diethyl ether (6 L). The mixture was washed with saturated brine (2.5 L), dried over sodium sulfate, and concentrated under reduced pressure. The residue was triturated successively with heptane (2 x 2 L), a 1:4 mixture of diethyl ether and heptane (2 L), and a 1:1 mixture of toluene and heptane (2.4 L) to give 8-methoxy-1-methylphenanthridin-6-amine (390 g, 55.7% yield after 3 steps) as a brown solid.

[0178] Methyl 3-bromo-4-oxobutanoate [ka] Bromine (21.6 mL, 0.421 mol, 1 equiv.) was added to a solution of ethyl 4-oxobutanoate (48.9 g, 0.421 mol, 1 equiv.) in dichloromethane (1.8 L). The reaction was stirred at room temperature for 45 min and then concentrated under reduced pressure at 5-8° C. The residual yellow thick oil (83 g) methyl 3-bromo-4-oxobutanoate was used in the next step without further purification.

[0179] Methyl 2-(11-methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)acetate [ka] A solution of methyl 3-bromo-4-oxobutanoate (83 g, 0.84 mol, 1.25 equiv.) in acetonitrile (0.75 L) was added to a suspension of 8-methoxy-1-methylphenanthridin-6-amine (160 g, 0.67 mol) and sodium bicarbonate (142 g, 1.69 mol, 2.5 equiv.) in a 6:1 mixture of acetonitrile and THF (7 L) at 40° C. After refluxing for 18 h, the reaction mixture was cooled to 5° C. and filtered. The filtrate was concentrated under reduced pressure and the resulting solid was triturated with a 1:1 mixture of diethyl ether and heptane (1 L) and filtered. The filter cake was washed with a 1:2.5 mixture of diethyl ether and heptane (0.7 L), dried, and dissolved in dichloromethane (1.3 L). The resulting solution was dried over sodium sulfate (50 g) and concentrated under reduced pressure to give methyl 2-(11-methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)acetate (139 g, 62% yield) as a light brown solid.

[0180] 2-(11-Methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)-2-methylpropanate [ka] Lithium bis(trimethylsilyl)amide, 1M in THF (1.7 L, 1.7 mol, 4 equiv.) was added dropwise to a solution of methyl 2-(11-methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)acetate (139 g, 0.416 mol, 1 equiv.) in anhydrous THF (2 L) at 0° C. The reaction was stirred at room temperature for 1 h. Methyl iodide (105 mL, 1.7 mol, 4 equiv.) was added dropwise at 0° C. After stirring at room temperature for 2 h, the reaction was quenched with methanol (0.1 L). The reaction mixture was diluted with dichloromethane (1 L) and water (1 L). After layer separation, the organic layer was washed with water (1 L) and saturated brine (0.8 L), dried over sodium sulfate (50 g), and concentrated under reduced pressure. The residue was dissolved in 5% methanol in dichloromethane (1 L) and filtered through a plug of silica gel (250 g). The filtrate was dried over sodium sulfate (50 g) and concentrated under reduced pressure. The residue was dissolved in toluene (2 L) and filtered. The insoluble material was discarded and the filtrate was concentrated under reduced pressure to give methyl 2-(11-methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)-2-methylpropanoate (136.5 g, 91% yield) as a pale yellow solid.

[0181] 3-(11-Methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)-3-methylbutan-2-one [ka] 1.6 M methyllithium in diethyl ether (0.71 L, 1.13 mol, 3 equiv.) was added slowly over 2.5 h at -30°C to a suspension of methyl 2-(11-methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)-2-methylpropanoate (136.5 g, 0.38 mol, 1 equiv.) in anhydrous THF (2 L). After stirring for an additional 3 h at -20°C, the reaction was quenched with methanol (50 mL). The reaction mixture was diluted with dichloromethane (1 L) and water (1 L). After layer separation, the organic layer was washed with water (1 L), saturated brine (0.8 L), dried over sodium sulfate (100 g), and concentrated under reduced pressure. The residue was azeotroped from toluene (250 mL) to give 3-(11-methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)-3-methylbutan-2-one (102.9 g, 79% yield) as a pale yellow solid.

[0182] 3-(2,3-dimethylbut-3-en-2-yl)-11-methoxy-8-methylimidazo[1,2-f]phenanthridine [ka] Potassium tert-butoxide (106.8 g, 0.952 mol, 3.2 equiv.) was added to a suspension of methyltriphenylphosphonium bromide (318.7 g 0.892 mol, 3 equiv.) in anhydrous THF (2.9 L) at room temperature. After stirring for 40 min, 3-(11-methoxy-8-methylimidazo[1,2-f]phenanthridin-3-yl)-3-methylbutan-2-one (102.9 g, 0.297 mol, 1 equiv.) was added and the reaction was stirred at 58° C. for 17 h. The reaction mixture was diluted with water (1.5 L) and dichloromethane (2 L). After layer separation, the organic layer was washed with water (1 L), saturated brine (1 L), dried over sodium sulfate (200 g), and concentrated under reduced pressure. The residue was purified on silica gel (500 g) eluted with a gradient of 25 to 60% ethyl acetate in heptane to give 3-(2,3-dimethylbut-3-en-2-yl)-11-methoxy-8-methylimidazo[1,2-f]phenanthridine (81.1 g, 79% yield).

[0183] 10-Methoxy-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine [ka] 3-(2,3-Dimethylbut-3-en-2-yl)-11-methoxy-8-methylimidazo[1,2-f]phenanthridine (119.3 g, 0.387 mol, 1.0 equiv.) was added to Eaton's reagent (1 L). The reaction was stirred at room temperature for 20 h. The reaction mixture was carefully poured onto ice and neutralized with 50% aqueous sodium hydroxide. The aqueous mixture was extracted with dichloromethane (2×2 L). The combined organic layers were dried over sodium sulfate (200 g) and concentrated under reduced pressure to give 10-methoxy-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine (116.1 g, 97% yield) as a bright yellow solid.

[0184] 3,3,4,4,7-Pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizin-10-ol [ka] 1M boron tribromide in dichloromethane (950 mL, 0.95 mol, 4 equiv.) was added dropwise to a solution of 10-methoxy-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine (80 g, 233 mmol, 1.0 equiv.) in dichloromethane (2.3 L) at -78°C. The reaction was allowed to warm to room temperature and stirred overnight. The reaction was quenched by careful addition of methanol (0.8 L) followed by 1M sodium hydroxide (1.6 L). The resulting mixture was stirred vigorously for 1 h. The organic layer was separated, washed with saturated brine (1 L), dried over sodium sulfate and concentrated under reduced pressure to give 3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizin-10-ol (77 g, 100% yield, 95% purity) as a pale yellow solid.

[0185] 10-(4-Fluoro-3-(1-(tetrahydro-2H-pyran-2-yl)-1H-imidazol-2-yl)phenoxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine [ka] 2-(5-Bromo-2-fluorophenyl)-1-(tetrahydro-2H-pyran-2-yl)-1H-imidazole (1.11 g, 3.41 mmol), 3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizin-10-ol (1.13 g, 3.41 mmol), picolinic acid (0.630 g, 5.12 mmol), copper(I) iodide (0.195 g, 1.02 mmol), and tripotassium phosphate monohydrate (2.75 g, 11.95 mmol) were combined and dissolved in DMSO (30 mL), after which the reaction vessel was sealed with a septum, degassed by continuous evacuation, and flushed with N. 2 Refilled with N 2 The flask was heated to 150° C. under atmospheric conditions and stirred for 16 h. The reaction was cooled to room temperature and the mixture was transferred to a separatory funnel containing DCM and saturated NH 4The mixture was diluted with 100 mL of ethyl acetate and diluted with 100 mL of ethyl acetate. The layers were separated and the aqueous layer was extracted with DCM. The combined organics were washed with water and brine. Drying (Na 2 SO 4 ), filtration, and concentration to a crude oil which was purified by column chromatography to give 1.42 g (72% yield) of 10-(4-fluoro-3-(1-(tetrahydro-2H-pyran-2-yl)-1H-imidazol-2-yl)phenoxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine as a white solid.

[0186] 10-(4-Fluoro-3-(1H-imidazol-2-yl)phenoxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine [ka] 4-Methylbenzenesulfonic acid hydrate (0.079 g, 0.415 mmol) was weighed into a flask containing 10-(4-fluoro-3-(1-(tetrahydro-2H-pyran-2-yl)-1H-imidazol-2-yl)phenoxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine (1.42 g, 2.47 mmol) and a stir bar. After adding methanol (40 mL), the mixture was heated to 70° C. and stirred overnight. After cooling to room temperature, 1.0 mL of triethylamine was added. The reaction mixture was concentrated and purified by column chromatography to give the desired 10-(4-fluoro-3-(1H-imidazol-2-yl)phenoxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine in 88% purity (79% yield) as 1.15 g of an off-white solid. A 12% impurity was identified as starting material and could be removed by further column chromatography or remained in the reaction for further steps.

[0187] 2-(1H-imidazol-2-yl)-N-isobutyl-4-((3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizin-10-yl)oxy)aniline [ka] 10-(4-Fluoro-3-(1H-imidazol-2-yl)phenoxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine was suspended in diglyme (40 ml) followed by the addition of isobutylamine (20 ml, 201 mmol). The reaction was degassed by rapid successive degassing / refilling cycles followed by the addition of isopropylmagnesium chloride (6 ml, 12.00 mmol). The reaction mixture was then heated to 110° C. for 3 h followed by heating to 150° C. overnight. After cooling to rt, it was quenched with water. After solvent removal, it was dissolved in DCM, transferred to a separatory funnel and diluted with saturated NH 4 The combined organics were washed with brine and dried (Na 2 SO 4 ), filtered, concentrated, and purified by column chromatography to give 0.29 g (40%) of 2-(1H-imidazol-2-yl)-N-isobutyl-4-((3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizin-10-yl)oxy)aniline as an off-white solid.

[0188] 5-(2,6-Dimethylphenyl)-6-isopropyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine [ka] 2-(1H-imidazol-2-yl)-N-isopropylaniline (250 mg, 1.242 mmol) was placed in a Schlenk flask and heated under vacuum / N 2The flask was cycled through three times. THF (4 mL) was added to give a clear, colorless solution which was cooled to -78 °C, followed by the dropwise addition of butyllithium (2.0 M in cyclohexane, 1.25 ml, 2.50 mmol) and the solution was allowed to stir at -78 °C for 1 h. A separate Schlenk flask was charged with potassium 2,6-dimethylphenyltrifluoroborate (280 mg, 1.320 mmol). Vacuum / N 2 After cycling through 3 times, THF (4 mL) was added, giving a clear, colorless solution. A solution of lithium chloride (0.5 M in THF, 3.00 ml, 1.500 mmol) was added via syringe, and the mixture was stirred at RT for 30 min, giving a pale yellow, slightly cloudy solution. This mixture was then added dropwise via syringe to the dianion, and the resulting mixture was placed in an oil bath at 50 °C for 16 h, then cooled to RT and saturated NH 4 The mixture was quenched with aqueous Cl and extracted with 3×20 mL of DCM. The organics were combined and washed with Na 2 SO 4 The mixture was dried over ice. Removal of the solvent gave a gummy yellow residue which was purified by column chromatography to give 306 mg (78%) of a colorless crystalline solid.

[0189] 5-(2,6-diisopropylphenyl)-8-methyl-6-phenyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine [ka] 2-(1H-imidazol-2-yl)-5-methyl-N-phenylaniline (1.00 g, 4.01 mmol) was placed in a 250 mL Schlenk tube and heated under vacuum / N 23 times. Anhydrous THF (10 mL) was added, giving a colorless solution. Cooled to -78 °C and butyllithium (2M in cyclohexane, 4.00 mL, 8.00 mmol) was added dropwise. Stirred at -78 °C for 1 h. During this time, a separate Schlenk flask was charged with solid lithium chloride (210 mg, 4.95 mmol) and heated with a heat gun under vacuum for 5 min. Potassium 2,6-diisopropylphenyltrifluoroborate (1.13 g, 4.21 mmol) was added, followed by 15 mL of THF. After stirring the dianion for 1 h, the trifluoroborate / lithium chloride mixture was transferred via cannula and the mixture was allowed to warm to RT. Stirred at RT for 1 h, then heated to 50 °C for 16 h. Cooled to RT and saturated NH 4 The mixture was quenched with aqueous Cl. It was extracted three times with DCM and the organics were combined and diluted with Na 2 SO 4 The mixture was dried over ice. Removal of the solvent gave a yellow residue, which was purified by column chromatography to give a colorless solid (1.32 g, 78%).

[0190] 5-(2,6-Dimethylphenyl)-6-isopropyl-5,6-dihydroimidazo[1,2-c]pyrido[3,2-e][1,3,2]diazaborinine [ka] 3-(1H-imidazol-2-yl)-N-isopropylpyridin-2-amine (200 mg, 0.989 mmol) was placed in a Schlenk tube and vacuum / N 2 The flask was cycled three times, followed by the addition of 4 mL of THF to give a brown solution. It was cooled to -78 °C and butyllithium (2 M in cyclohexane, 1.00 ml, 2.000 mmol) was added dropwise. It was stirred at -78 °C for 15 min. During this time, potassium 2,6-dimethylphenyltrifluoroborate (231 mg, 1.089 mmol) was placed in a separate Schlenk flask and vacuum / N 23 times. 1.5 mL of THF was added, followed by lithium chloride (0.5 M in THF, 2.5 ml, 1.250 mmol) solution via syringe. Stirred at rt for 10 min. Then the trifluoroborate / lithium chloride mixture was added dropwise via syringe to the bis-amide solution at -78 °C, and the mixture was heated to 50 °C for 16 h. Cooled to RT and saturated NH 4 The mixture was quenched with aqueous Cl. It was extracted three times with DCM and the organics were combined and diluted with Na 2 SO 4 The mixture was dried over ice. Removal of the solvent gave a yellow residue which was purified by column chromatography to give a colorless solid (192 mg, 61%).

[0191] 6-(2,6-diisopropylphenyl)-5-methyl-5,6,8,9,10,11-hexahydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaborinine [ka] Place N-methyl-2-(4,5,6,7-tetrahydro-1H-benzo[d]imidazol-2-yl)aniline (525 mg, 2.310 mmol) in a 250 mL Schlenk tube and evacuate under vacuum / N 2 3 times. Anhydrous THF (20 mL) was added, giving a yellow solution. Cooled to -78 °C and butyllithium (2M in cyclohexane, 2.35 ml, 4.70 mmol) was added dropwise. Stirred at -78 °C for 1 h. During this time, a separate Schlenk flask was charged with solid lithium chloride (196 mg, 4.62 mmol) and heated with a heat gun under vacuum for 5 min. Potassium 2,6-diisopropylphenyltrifluoroborate (867 mg, 3.23 mmol) was added, followed by 10 mL of THF. After stirring the dianion for 1 h, the trifluoroborate / lithium chloride mixture was transferred via cannula and the mixture was allowed to warm to RT. Stirred at RT for 1 h, then heated to 50 °C for 16 h. Cooled to RT and saturated NH 4 The mixture was quenched with aqueous Cl. It was extracted three times with DCM and the organics were combined and diluted with Na 2 SO 4The mixture was dried over ice. Removal of the solvent gave a yellow residue, which was purified by column chromatography to give a colorless solid (740 mg, 81%).

[0192] 5-(2,6-dimethylphenyl)-6-methyl-2-phenyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine [ka] Potassium 2,6-dimethylphenyltrifluoroborate (55 mg, 0.259 mmol) and N-methyl-2-(4-phenyl-1H-imidazol-2-yl)aniline (50 mg, 0.201 mmol) were placed in a separate Schlenk flask and cooled under vacuum / N 2 After cycling through 3 times, 1 mL of THF was added to each, giving a colorless solution. To the trifluoroborate salt solution, a 0.5 M solution of lithium chloride (0.550 ml, 0.275 mmol) in THF was added and stirred at RT for 20 min. During this time, the imidazoloaniline solution was cooled to -78 °C, and then butyllithium (1.6 M in hexanes, 0.260 ml, 0.416 mmol) was added dropwise to give a light yellow solution. After stirring at -78 °C for 20 min, the trifluoroborate / lithium chloride mixture was added dropwise via syringe to give a light green mixture, which turned yellow after warming to RT. Heat to 60 °C for 24 h. Cool to RT and add saturated NH 4 After quenching with aqueous Cl, the mixture was extracted three times with DCM. 2 SO 4 Drying over and removal of solvent gave a yellow foam which was purified by column chromatography to give 35 mg (48%) of a colorless foam.

[0193] 5-([1,1':3',1''-terphenyl]-2'-yl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine [ka] A solution of [1,1':3',1''-terphenyl]-2'-ylboronic acid (1.6 g, 5.3 mmol) and 2-(1H-imidazol-2-yl)-N-methylaniline (1.0 g, 5.8 mmol) in xylene (25 mL) was heated to reflux in a graduated Dean-Stark apparatus equipped with a stopcock. The Dean-Stark trap was drained through the stopcock every hour for 6 h (fresh xylene was added when the reaction was dry). The reaction mixture was heated to reflux for 24 h and then concentrated. The residue was suspended in DCM (10 mL) and filtered. The filtrate was purified by column chromatography to give 5-([1,1':3',1''-terphenyl]-2'-yl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine (1.6 g, 3.9 mmol, 73% yield, 99.6% HPLC) as a colorless solid.

[0194] 5-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine [ka] A solution of (3,5-diisopropyl-[1,1'-biphenyl]-4-yl)boronic acid (2.1 g, 7.4 mmol) and 2-(1H-imidazol-2-yl)-N-methylaniline (1.5 g, 8.7 mmol) in xylene (50 mL) was heated to reflux for 1 h in a graduated Dean-Stark apparatus equipped with a stopcock. The Dean-Stark trap was drained (removing 12 mL of xylene), reflux was continued for an additional hour, and the trap was drained again (12 mL). The reaction was cooled and fresh xylene (50 L) was added. Reflux was continued and an additional 12 mL of xylene was drained from the trap before refluxing continued overnight. Nearly all the solvent had left the apparatus leaving a brown crystalline solid. This material was suspended in DCM (50 mL) and the solid removed by filtration. The filtrate was purified by column chromatography to give 5-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine (2.1 g, 5.0 mmol, 67% yield, 99.5% HPLC) as a colorless solid.

[0195] 5-(2,6-diisopropylphenyl)-6-methyl-2,3-diphenyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine [ka] To a solution of 2-(4,5-diphenyl-1H-imidazol-2-yl)-N-methylaniline (3.12 g, 9.59 mmol) in THF (40 mL) at −78° C. nBuLi (2.1 M in hexanes, 9.0 mL, 19 mmol) was added dropwise and the mixture was stirred at this temperature for 30 min (mixture 1). Meanwhile, to a solution of potassium (2,6-diisopropylphenyl)trifluoroborate (2.70 g, 10.1 mmol) in dry THF (20 mL) was added TMS-Cl (1.3 mL, 11 mmol) and the mixture was stirred at RT for 15 min (mixture 2). Mixture 2 was added dropwise to mixture 1 and the reaction mixture was allowed to warm to RT and then stirred at 60° C. for 3 h. The reaction mixture was cooled to RT, diluted with water (100 mL) and extracted with EtOAc (3×250 mL). The combined organic extracts were concentrated to give crude 5-(2,6-diisopropylphenyl)-6-methyl-2,3-diphenyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine (3.04 g, 5.09 mmol, 54% yield, 83% UPLC purity) as a white solid. Five batches of 5-(2,6-diisopropylphenyl)-6-methyl-2,3-diphenyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine (3.0 g, 83% purity; 0.3 g, 92% purity; 0.5 g, 94% purity; 0.6 g, 98% purity; 0.2 g, 83% purity) were completely dissolved in hot THF (30 mL). The THF was evaporated and the residue was suspended in MeCN (6 mL) and stirred for 30 min. The solid was collected by filtration, resuspended in MeCN (10 mL) and stirred for 30 min. The solid was collected by filtration and dried in a vacuum desiccator to give 5-(2,6-diisopropylphenyl)-6-methyl-2,3-diphenyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine (3.92 g, 7.88 mmol, 85% yield, 99.6% HPLC) as a white solid.

[0196] 9-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-5-(2,6-diisopropylphenyl)-6-phenyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine [ka] Lithium chloride (.11 g, 2.59 mmol) and (2,6-diisopropylphenyl)trifluoro-14-borane, potassium salt (.48 g, 1.790 mmol) were dissolved in N 2 Dissolved in anhydrous THF (10 ml) under atmospheric pressure. The resulting cloudy solution was stirred at rt for 30 min. Concurrently, 4-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2-(1H-imidazol-2-yl)-N-phenylaniline (.68 g, 1.237 mmol) was dissolved in anhydrous THF (10 ml) and cooled to -78°C. n-Butyllithium (1.3 ml, 2.60 mmol) was added via syringe and the resulting solution was stirred at -78°C for 30 min, at which point the boronate / LiCl solution was transferred via cannula. The combined mixture was stirred at -78°C for an additional 5 min, then warmed to rt and then heated to 60°C overnight. After cooling the reaction to rt, NH 4 The mixture was quenched with aqueous Cl. It was diluted with DCM and water and transferred to a separatory funnel. After separation of the layers, the aqueous layer was extracted with DCM. The combined organics were washed with brine and dried (Na 2 SO 4 ), filtered, concentrated, and purified by column chromatography to give 0.65 g (73% yield) of 9-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-5-(2,6-diisopropylphenyl)-6-phenyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine as a white solid.

[0197] 10-((5-(2,6-diisopropylphenyl)-6-isobutyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborin-9-yl)oxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine [ka] Lithium chloride (0.069 g, 1.63 mmol) and (2,6-diisopropylphenyl)trifluoro-14-borane, potassium salt (0.200 g, 0.747 mmol) were dissolved in N 2 The resulting cloudy solution was stirred at rt for 45 min. Concurrently, 2-(1H-imidazol-2-yl)-N-isobutyl-4-((3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizin-10-yl)oxy)aniline (.29 g, 0.533 mmol) was dissolved in anhydrous THF (40 ml) and cooled to -78°C. n-Butyllithium (0.6 ml, 2.60 mmol) was added via syringe and the resulting solution was stirred at -78°C for 30 min, at which point the boronate / LiCl solution was transferred via cannula. The combined mixture was stirred at -78°C for an additional 5 min, then warmed to rt and then heated to 60°C overnight. After cooling the reaction to rt, NH 4 The mixture was quenched with aqueous Cl. It was diluted with DCM and water and transferred to a separatory funnel. After separation of the layers, the aqueous layer was extracted with DCM. The combined organics were washed with brine and dried (Na 2 SO 4 ), filtered, concentrated, and purified by column chromatography to give 0.302 g (79% yield) of 10-((5-(2,6-diisopropylphenyl)-6-isobutyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborin-9-yl)oxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine as a white solid.

[0198] 5-(2,4,6-tri-tert-butylphenyl)-5H-benzo[e]imidazo[1,2-c][1,3,2]oxazaborinine [ka] Dimethyl(2,4,6-tri-tert-butylphenyl)boronate (.727 g, 2.284 mmol) was dissolved in N 2This was combined with iron(III) chloride (.018 g, 0.111 mmol) under atmospheric pressure and dissolved in anhydrous dichloromethane (15 ml). The resulting mixture was cooled to 0° C. After the addition of trichloroborane (1.0 M in heptane, 4.6 ml, 4.60 mmol), the reaction was stirred at 0° C. for 1 h, then warmed to rt and stirred for 3 h. The volatile solvents and reagents were removed by vacuum distillation, and then anhydrous toluene (20 ml) was added, followed by 2-(1H-imidazol-2-yl)phenol (0.366 g, 2.284 mmol) and 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (DBU, 1.025 ml, 6.85 mmol). The reaction mixture was then diluted with N 2 The reaction was refluxed overnight at room temperature for 10 min. The reaction was cooled to rt, concentrated, and purified directly by column chromatography to give 0.248 g (26%) of 5-(2,4,6-tri-tert-butylphenyl)-5H-benzo[e]imidazo[1,2-c][1,3,2]oxazaborinine as a colorless oil that slowly crystallized to a white solid.

[0199] 2,3-Diphenyl-5-(2,4,6-tri-tert-butylphenyl)-5H-benzo[e]imidazo[1,2-c][1,3,2]oxazaborinine [ka] Dimethyl(2,4,6-tri-tert-butylphenyl)boronate (1.77 g, 5.56 mmol) was dissolved in N 2Combine with iron(III) chloride (.065 g, 0.401 mmol) under atmospheric pressure and dissolve in anhydrous dichloromethane (15 ml). The resulting mixture was cooled to 0° C. Trichloroborane (1.0 M in heptane, 14 ml, 14.00 mmol) was added and the reaction was stirred at 0° C. for 1 h before warming to rt and stirring for 22 h. Volatile solvents and reagents were removed by vacuum distillation and then anhydrous toluene (20 ml) was added followed by 2-(4,5-diphenyl-1H-imidazol-2-yl)phenol (1.737 g, 5.56 mmol) and 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (DBU, 3.0 ml, 20 mmol). The reaction mixture was cooled to 0° C. with 5% CO.sub.2O, 10% CO.sub.2O, and 10% CO.sub.2O. 2 The reaction was refluxed overnight at room temperature for 20 min. The reaction was cooled to rt and directly purified by column chromatography to give 0.245 g (7.8%) of 2,3-diphenyl-5-(2,4,6-tri-tert-butylphenyl)-5H-benzo[e]imidazo[1,2-c][1,3,2]oxazaborinine as a white solid.

[0200] 2-Bromo-3,5-dimethylpyridine [ka] 2-(Dimethylamino)ethan-1-ol (5.37 ml, 53.4 mmol) was dissolved in heptane (250 ml) under nitrogen and cooled in an ice / water bath. Butyllithium (2.5 M solution in hexanes, 42.7 ml, 107 mmol) was added in portions resulting in a pale yellow cloudy mixture. After stirring cold for 30 minutes, 3,4-dimethylpyridine (5 ml, 44.5 mmol) was added slowly producing a yellow precipitate. The mixture was stirred cold for 1 hour and then cooled. i PrOH / CO 2Cooled in bath. Separately, perbromomethane (22.14 g, 66.8 mmol) was dissolved in THF (50 ml) and added via cannula, producing a dark mass that required manual stirring. Stirred again and allowed the mixture to warm to room temperature, stirred for 16 hours, and quenched with water and brine. The mixture was extracted three times with EtOAc and the combined organics were washed with brine, dried, and concentrated in vacuo. The residue was purified by column chromatography to give 2.10 g (25%) of a yellow / brown oil that contained approximately 10% isomeric impurity. This material was used without further purification.

[0201] 9-(4,5-Dimethylpyridin-2-yl)-9H-carbazole [ka] 2-Bromo-4,5-dimethylpyridine (2.112 g, 11.35 mmol) (~90% purity), 9H-carbazole (1.46 g, 8.73 mmol), lithium 2-methylpropan-2-olate (1.398 g, 17.46 mmol), and copper(I) iodide (0.665 g, 3.49 mmol) were combined in a nitrogen flushed flask. 1-Methyl-1H-imidazole (0.693 ml, 8.73 mmol) was added via syringe and toluene (21.83 ml) was added via cannula. The dark brown mixture was refluxed for 3 days and then partitioned between aqueous NH4Cl and EtOAc. Concentration and purification by column chromatography gave 1.91 g of an almost white solid (80%).

[0202] [(NBN) 2 IrCl] 2 Representative synthesis: [ka] IrCl 3 (MeCN) 3(0.170 g, 0.403 mmol) and 5-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine (0.507 g, 1.209 mmol) were combined in diglyme (3 mL) and the mixture was refluxed for 16 h. The mixture was cooled to room temperature and 3 mL of MeOH was added. After filtration and washing with MeOH, 345 mg of the iridium dimer was obtained as a yellow solid (80%).

[0203] Solvent-[IrL 2 Representative synthesis of OTf: [ka] Iridium dimer (0.650 g, 0.305 mmol) was dissolved in DCM (25 ml) and a solution of silver triflate (0.161 g, 0.626 mmol) in MeCN (3.57 ml) was added and the mixture was stirred at room temperature for 16 h, covered in foil. The nearly colorless suspension was filtered through Celite, which was washed with DCM / MeCN. After removal of the solvent, azeotrope from DCM / heptane gave a pale yellow solid (quantitative yield).

[0204] Representative synthesis of Ir(NBN)2(PyCz): [ka] Solvent-[IrL 2 ]OTf (0.027 g, 0.021 mmol) and 9-(4,5-dimethylpyridin-2-yl)-9H-carbazole (0.012 g, 0.043 mmol) were combined in a Schlenk flask under nitrogen. Triethylamine (5.97 μl, 0.043 mmol) and dioxane (1 ml) were added via syringe and the mixture was heated to reflux for 16 h. The solvent was removed under vacuum and the residue was coated onto Celite. Purification by column chromatography afforded 10 mg of Ir[L Aa 12-B(76)(1)(15)(15)] 2 [L BB164 ] was obtained as a yellow solid (36%).

[0205] Ir(L) 3 Representative synthesis of the complex: [ka] 5-(3,5-Diisopropyl-[1,1'-biphenyl]-4-yl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine (0.048 g, 0.114 mmol) and the iridium precursor (0.015 g, 0.033 mmol; Brooks et al., US20180090691) were combined in phenol (0.5 ml) under nitrogen and the mixture was heated to reflux for 16 h. Purification by column chromatography afforded Ir[L Aa 12-B(76)(1)(15)(15)] 3 was obtained as a yellow solid.

[0206] Ir(L BB139 ) 2 Synthesis of (acac): [ka] A solution of 4,4-dimethyl-3,3,7-tris(methyl-d3)-2-phenyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine (19.24 g, 48.2 mmol) in 1,2-dichlorobenzene (120 ml) was sparged with nitrogen for 10 minutes and then diluted with Ir 2 (acac) 6 (11.5 g, 11.75 mmol) was added and sparged with nitrogen for an additional 10 min. The reaction was heated at 180° C. for 24 h. Column chromatography followed by trituration in MeOH gave 12 g (47%) of product as a light yellow solid.

[0207] Solvent-[Ir(L BB139 ) 2 Synthesis of OTf complexes: [ka] IrL 2The (acac) complex (10 g, 9.19 mmol) was suspended in acetonitrile (40 ml). Trifluoromethanesulfonic acid (1.784 ml, 20.21 mmol) dissolved in 5 ml of acetonitrile was added dropwise to the mixture at room temperature to obtain a homogeneous solution, which was stirred for 24 hours. The mixture was concentrated under reduced pressure, and the precipitate was collected by filtration and washed with small portions of MTBE until the filtrate was colorless to give 6.9 g of the product as a colorless solid (61%).

[0208] Ir(L BB139 ) n (NBN) 3-n Representative synthesis of the complex: [ka] Solvent-[IrL 2 The ]OTf complex (1 g, 0.819 mmol) and 5-(2,6-dimethylphenyl)-6-(methyl-d3)-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinine (0.476 g, 1.639 mmol) were mixed together in 1,2-dichlorobenzene (15 ml) in a pressure tube and sparged with Ar for 10 min. The tube was sealed and stirred at 140 °C for 16 h. The reaction mixture was coated onto Celite and purified by column chromatography on silica gel followed by reverse phase chromatography to give both complexes in >99% purity.

[0209] Representative synthesis of tetradentate-(L)Pt: [ka] 10-((5-(2,6-diisopropylphenyl)-6-isobutyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborin-9-yl)oxy)-3,3,4,4,7-pentamethyl-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinolizine (0.302 g, 0.423 mmol) and Pt(II) acetylacetonate (0.170 g, 0.432 mmol) were dissolved in 1,2-dichlorobenzene (2.0 mL). The resulting solution was stirred for 1 hour at 37° C. for 24 hours at 37° C. for 1 hour at 37° C. for 24 hours at 37° C. for 24 hours at 37° C. The solution was stirred for 1 hour at 37° C. for 24 hours ... for 24 hours at 37° C. The solution was stirred for 1 hour at 37° C. for2 ) and then degassed with N 2 The reaction was heated to reflux under atmosphere for 3 days. The mixture was cooled to rt, concentrated and then directly purified by column chromatography to give the metal complex as a yellow solid. [Table 1] The structures of the compounds in Table 1 are shown below. [ka] [ka] [ka] [ka] [ka] b) Preparation of exemplary devices of the present disclosure [ka]

[0210] The OLEDs were grown on glass substrates precoated with a 15-Ω / sq. indium tin oxide (ITO) layer. Prior to deposition or coating of the organic layers, the substrates were degreased with solvent and then treated with oxygen plasma for 1.5 min at 50 W and 100 mTorr and UV ozone for 5 min. All devices were grown in a nitrogen glove box (H 2 O and O 2 The device was encapsulated with a glass lid sealed with epoxy resin to within 1 ppm of the doping percentage (<1 ppm) and a moisture getter was placed inside the package. The doping percentage is by volume.

[0211] Each device in Table 2 was prepared by thermal evaporation under high vacuum (<10-6 Torr). The anode electrode was 750 Å of indium tin oxide (ITO). The organic layers of the device example consisted of, from the ITO surface, 100 Å thick compound 1 (HIL), a 250 Å layer of compound 2 (HTL), 300 Å of compound 3 (EML) doped with the indicated percentage of light-emitting compound, 50 Å of compound 4 (EBL), 300 Å of compound 7 (ETL), 10 Å of compound 8 or LiF (electron / exciton injection layer), and 1,000 Å of Al (cathode). [Table 2]

[0212] Each device in Table 3 was prepared by thermal evaporation under high vacuum (<10-6 Torr). The anode electrode was 750 Å of indium tin oxide (ITO). The organic layers of the device example consisted of, from the ITO surface, 100 Å thick compound 1 (HIL), a 250 Å layer of compound 2 (HTL), 300 Å of compound 3 doped with 20% compound 5, 10% compound 6, and 12% phosphor (EML), 50 Å of compound 4 (EBL), 300 Å of compound 7 (ETL), 10 Å of compound 8 or LiF (electron / exciton injection layer), and 1,000 Å of Al (cathode). [Table 3]

[0213] As the data in Table 2 show, the iridium compounds of the present invention exhibit superior electroluminescence lifetimes compared to Comparative Compound 1. These lifetime increases of up to 5.3 times and EQE increases of up to 4.5 times are observed across a wide range of both N- and B-substitutions, again demonstrating that the iridium compounds of the present invention are superior iridium-based phosphorescent dopants. Furthermore, these desirable electroluminescence properties are consistent with the λ max This can be accompanied by a blue shift of up to 5 nm in the emission line, making the compounds of the present invention more suitable for display applications targeting a more saturated deep blue color point.

[0214] The Pt compounds of the present invention in Table 3 are shown to have similar colors but narrower FWHMs than the Ir compounds. Thus, like the iridium compounds, the platinum compounds of the present invention are promising candidates for deep blue emitting electroluminescent applications.

[0215] It is understood that the various embodiments described herein are merely exemplary and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. Thus, the invention as claimed may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that the various theories of why the invention works are not intended to be limiting. [Explanation of symbols]

[0216] 100 Organic Light Emitting Device 110 Substrate 115 Anode 120 Hole injection layer 125 Hole transport layer 130 Electron Blocking Layer 135 Light-emitting layer 140 Hole Blocking Layer 145 Electron transport layer 150 Electron injection layer 155 Protective layer 160 Cathode 162 First conductive layer 164 Second conductive layer 170 Barrier Layer 200 Inverted OLED, device 210 Substrate 215 Cathode 220 Light-emitting layer 225 Hole transport layer 230 Anode

Claims

1. Ligand L of formula I Ａ A compound comprising: 【Chemistry 1】 (In the formula, Ring A and Ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; Z １ ~Z ５ are each independently C or N; X is BR １ , B.R. １ R ２ , AlR １ , AlR １ R ２ , GaR １ , GaR １ R ２ , InR １ , InR １ R ２ , CO, SO ２ , or P.O.R. １ and Y is NR ３ , N.R. ３ R ４ , P.R. ３ ,O,S,SO,SO ２ , C.R. ３ R ４ , SiR ３ R ４ , P.R. ３ R ４ , or GeR ３ R ４ and R Ａ and R Ｂ each represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R Ａ , R Ｂ , R １ , R ２ , R ３ , and R ４ each is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; Any two substituents may be bonded or fused together to form a ring; The ligand L Ａ is coordinated to the metal M by two labeled wavy lines; The ligand L Ａ can combine with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands.

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

3. The compound has the following formula IA: 【Chemistry 2】 (In the ceremony Z １ ~Z ４ at least two of are C; X is BR １ and Y is NR ３ or O, or X is BR １ R ２ and Y is NR ３ R ４ and R １ , R ２ , R ３ , and R ４ each is independently selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, silyl, boryl, aryl, heteroaryl, alkoxy, aryloxy, amino, and combinations thereof; The remaining variables are the same as previously defined. X is BR １ and Y is NR ３ When B.R. １ R １ But, N.R. ３ R ３ The two substituents can be linked to form a ring, except that they do not form a ring with the ligand L Ａａ Including, Or the following formula IB: 【Chemistry 3】 (In the formula, X １ , X ２ , and X ３ are each independently C or N, at least two of which are C; Z １ and Z ５ one of is C and the other is N; the remaining variables are the same as previously defined; Ligand L Ａｂ is coordinated to the metal M; M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag, and Au; M can be coordinated to other ligands; Any two substituents may be joined or fused to form a ring; The ligand L Ａｂ Ligand L in the formula (I) can be linked with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands. Ａ 2. The compound of claim 1 comprising:

4. X is BR １ and Y is NR ３ The compound according to claim 2,

5. X is BR １ and R １ is represented by the following formula II: 【Chemistry 4】 wherein ring C is a 5- or 6-membered carbocyclic or heterocyclic ring; Z ６ , Z ７ , and Z ８ are each independently C or N; R Ｘ is R Ａ Or R Ｂ has the same definition as R ５ and R ６ are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; R ５ and R ６ At least one of is not hydrogen.

6. 4. The compound according to claim 2, wherein ring A is a 5-membered heterocycle and ring B is a 6-membered carbocycle or heterocycle.

7. The ligand L Ａ The compound of claim 1, wherein is selected from the group consisting of: 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 (In the formula, R Ｚ and R Ｃ is R Ａ Or R Ｂ has the same definition as ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , and R １７ is R １ ~R ４ (has the same definition as

8. The ligand L Ａ The compound of claim 1 , wherein is selected from the group consisting of the structures of LA List 1 below. 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 【Chemistry 18】 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 (In the formula, R Ａ i, R Ａ j, R Ａ k, R Ａ l, R Ａ m, R Ａ n, R Ａ O, R Ａ p, R Ａ q, R Ａ r, R Ａ x, R Ａ y and R Ａ z has the structure defined in RA List 1 below. 【Chemical 22】 【Chemistry 23】 【Chemistry 24】 (In the formula, L Ｑ s, L Ｑ t, L Ｑ u, L Ｑ v, and L Ｑ w has the structure defined in LQ Listing 1 below. 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemical 29】 【Chemistry 30】 【Chemistry 31】 【Chemistry 32】 【Chemical Formula 33】 【Chemical 34】 【Chemistry 35】

9. The ligand L Ａ The compound of claim 3, wherein is selected from the group consisting of: 【Chemical Formula 36】 【Chemical 37】 (In the formula, Y １ , O, S, NR ３ , P.R. ３ , C.R. ３ R ４ , and SiR ３ R ４ is selected from the group consisting of

10. The ligand L Ａ The compound of claim 3, wherein is selected from the group consisting of the structures defined in LA List 2 below. 【Chemical Formula 38】 【Chemical 39】 【Chemistry 40】 【Chemistry 41】 【Chemistry 42】 (In the formula, R Ａ i, R Ａ j, and R Ａ k has the structure defined below. 【Chemistry 43】

11. The compound has the formula M(L Ａ ) x (L Ｂ ) y(L Ｃ ) z, wherein L Ｂ and L Ｃ are each a bidentate ligand; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M.

12. L Ｂ and L Ｃ 12. The compound of claim 11, wherein each is independently selected from the group consisting of: 【Chemistry 44】 【Chemistry 45】 (In the formula, Y １ ~Y １３ each is independently selected from the group consisting of carbon and nitrogen; Y' is BR ｅ , N.R. ｅ , P.R. ｅ , O, S, Se, C=O, S=O, SO ２ , C.R. ｅ R ｆ , SiR ｅ R ｆ , and GeR ｅ R ｆ wherein R ｅ and R ｆ can be fused or linked to form a ring; R ａ , R ｂ , R ｃ , and R ｄ each independently represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R ａ , R ｂ , R ｃ , R ｄ , R ｅ , and R ｆ each is independently selected from the group consisting of hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R ａ , R ｂ , R ｃ , and R ｄ Any two adjacent substituents of may be fused or linked to form a ring or to form a multidentate ligand.

13. 4. The compound of claim 3, wherein the compound is selected from the group consisting of the structures in Compound List 1 below. 【Chemistry 46】 【Chemistry 47】 【Chemistry 48】 【Chemistry 49】 【Chemistry 50】 【Chemistry 51】 【Chemistry 52】 【Chemistry 53】

14. 2. The compound of claim 1 , wherein the compound has formula III: 【Chemical 54】 (In the formula, M is Pd or Pt; Rings C and D are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; M １ and M. ２ are each independently C or N; A １ ~A ３ are each independently C or N; K １ and K. ２ are each independently selected from the group consisting of a direct bond, O, and S; L １ ~L ３ are each independently selected from the group consisting of a direct bond, O, S, CR'R'', SiR'R'', BR', and NR'; R′ and R″ are each independently selected from the group consisting of hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; m, n, and o are each independently 0 or 1; m+n+o=2 or 3; R Ｃ and R Ｄ are R Ａ Or R Ｂ have the same definition; The remaining variables are the same as previously defined; Any two substituents can be bonded or fused together to form a ring.

15. 1. An organic light emitting device (OLED), comprising: An anode; A cathode; an organic layer disposed between the anode and the cathode, the organic layer comprising a first ligand L of formula I: Ａ 1. An organic light emitting device (OLED) comprising a compound comprising: 【Chemistry 55】 (In the formula, Ring A and Ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; Z １ ~Z ５ are each independently C or N; X is BR １ , B.R. １ R ２ , AlR １ , AlR １ R ２ , GaR １ , GaR １ R ２ , InR １ , InR １ R ２ , CO, SO ２ , or P.O.R. １ and Y is NR ３ , N.R. ３ R ４ , P.R. ３ ,O,S,SO,SO ２ , C.R. ３ R ４ , SiR ３ R ４ , P.R. ３ R ４ , or GeR ３ R ４ and R Ａ and R Ｂ each represents zero, mono, or up to the maximum number of substitutions allowed on its associated ring; R Ａ , R Ｂ , R １ , R ２ , R ３ , and R ４ each is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; Any two substituents may be bonded or fused together to form a ring; The ligand L Ａ is coordinated to the metal M by two labeled wavy lines; The ligand L Ａ can combine with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands.

Images