Organic electroluminescent materials and devices

Abstract

To provide organometallic compounds useful for organic light emitting diodes.SOLUTION: Provided are organometallic compounds including a ligand LA represented by formula I or II in the figure. In the formulas, ring A is independently a 5- to 10-membered heterocycle; X1-X6 are each independently C or N; K3 is a direct bond, O or S; R1, RA, RB and RC are each independently H, D, halogen, or the like; and the ligand LA is complexed with a metal M, such as Pd or Pt, through the two indicated dashed lines.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 63 / 087,062, filed October 2, 2020, and U.S. Provisional Application No. 63 / 193,755, filed May 27, 2021, the disclosures of both of which are incorporated herein by reference in their entireties.

[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. Because many of the materials used to fabricate such devices are relatively inexpensive, 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 conventional 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 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. Conventionally, liquid crystal display emission from a white backlight is filtered with absorption 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 stacked 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 method for producing a method of manufacturing a semiconductor device comprising: [ka] Ligand L A wherein ring A is independently a 5- to 10-membered heterocycle; X 1 ~X 6 are each independently C or N; K 3 is a direct bond, O, or S; the maximum number of N atoms bonded to each other in a ring is 2; R A , R B , and R C each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R, R A , R B , R C are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein, and the ligand L A is complexed with a metal M through two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can be coordinated to other ligands; the ligand L Acan combine with other ligands to form tridentate, tetradentate, pentadentate, hexadentate, or heptadentate ligands; any two adjacent R A , R B , R C , or R 1, wherein the compound is: [ka] can be linked or fused to form a ring, provided that the ring does not contain either of the structures shown in

[0007] In another aspect, the present disclosure provides a ligand L of Formula I or Formula II described herein. A A composition of compounds comprising:

[0008] In yet another aspect, the present disclosure provides a ligand L of Formula I or Formula II described herein. A An OLED is provided having an organic layer comprising a compound comprising:

[0009] In yet another aspect, the present disclosure provides a ligand L of Formula I or Formula II described herein. A The present invention provides a consumer product comprising an OLED having an organic layer comprising a compound comprising: [Brief explanation of the drawings]

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

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

[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 contain repeating units in some circumstances. For example, using a long-chain alkyl group as a substituent does not remove a molecule from the "small molecule" class. Small molecules 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 all dendrimers currently used in the field of OLEDs are considered to be 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 solution or suspension form.

[0016] A ligand may be referred to as "photoactive" if it is considered to directly contribute to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" if it is considered not to 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. Because ionization potentials (IPs) are measured as negative energies relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On a conventional energy level diagram 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, and 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. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a "higher" work function is illustrated as being farther away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

[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 ) refers to

[0021] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R sor -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 "selenyl" refers to SeR s Refers to the base.

[0025] The term "sulfinyl" refers to -S(O)-R s Refers to the base.

[0026] The term "sulfonyl" means -SO2-R s Refers to the base.

[0027] The term "phosphino" refers to -P(R s ) refers to three groups, each R s may be the same or different.

[0028] The term "silyl" refers to -Si(R s ) refers to three groups, each R s may be the same or different.

[0029] The term "germyl" refers to -Ge(R s ) refers to three groups, each R s may be the same or different.

[0030] The term "boryl" means -B(R s ) group or its Lewis adduct -B(R s ) 3 groups, R s may be the same or different.

[0031] In each of the above, R scan 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.

[0032] The term "alkyl" refers to and includes both straight-chain 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.

[0033] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups contain 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Furthermore, the cycloalkyl groups may be optionally substituted.

[0034] The terms "heteroalkyl" or "heterocycloalkyl" refer 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 or heterocycloalkyl group may be optionally substituted.

[0035] 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. As used herein, the term "heteroalkenyl" 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 group may be optionally substituted.

[0036] The term "alkynyl" refers to and includes both straight-chain and branched-chain alkyne groups. Alkynyl groups are essentially alkyl groups containing at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkynyl groups may be optionally substituted.

[0037] The terms "aralkyl" and "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. In addition, said aralkyl group may be optionally substituted.

[0038] 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 heteroaromatic cyclic groups contain 3 to 7 ring atoms and include at least one heteroatom, including cyclic amines such as morpholino, piperidino, and pyrrolidino, and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, and tetrahydrothiophene. Furthermore, the heterocyclic groups may be optionally substituted.

[0039] 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 in which two carbon atoms are shared between two adjacent rings (the rings are "fused"), at least one of which is an aromatic hydrocarbyl group, and the other rings can be, for example, a cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups contain 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 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.

[0040] 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 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; for example, 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 3 to 20 carbon atoms, and more preferably 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, and preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and their aza analogs. Furthermore, the heteroaryl group may be optionally substituted.

[0041] Of the aryl and heteroaryl groups listed above, 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.

[0042] 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.

[0043] In many instances, the typical substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.

[0044] In some instances, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

[0045] In some instances, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.

[0046] In still other instances, more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0047] 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 mono-substituted group, one R 1 must be other than H (i.e., a substitution). Similarly, R 1 If represents a di-substitution, R 1 must be other than H. Similarly, R 1 When represents zero or no substitution, R1 can be a hydrogen at an available valence of a ring atom, as in the case of a carbon atom in benzene and a nitrogen atom in pyrrole, or simply represent nothing in the case of a ring atom with a fully satisfied valence (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.

[0048] As used herein, "combinations thereof" refers to one or more members of the applicable list being combined to form known or chemically stable configurations that one skilled in the art can contemplate 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 arylalkyl. In one example, the term "substituted" includes combinations of 2 to 4 of the listed groups. In another example, the term "substituted" includes combinations of 2 to 3 groups. In yet another example, the term "substituted" includes combinations of 2 groups. Preferred combinations of substituents are those containing up to 50 atoms that are not hydrogen or deuterium, or those containing up to 40 atoms that are not hydrogen or deuterium, or those containing 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.

[0049] The designation "aza" in the fragments described herein, such as aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C—H groups in each aromatic ring can be replaced by a nitrogen atom; for example, but not by way of limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Those skilled in the art can readily envision other nitrogen analogs of the above-described aza derivatives, and all such analogs are intended to be encompassed by the terms described herein.

[0050] 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 entire contents of which are incorporated by reference, 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 entire contents of which are incorporated by reference, which describe efficient routes for deuteration of methylene hydrogens in benzylamines and substitution of aromatic ring hydrogens with deuterium, respectively.

[0051] It is understood that when a molecular fragment is described as being a substituent or as being 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 substituents or attached fragments are considered equivalent herein.

[0052] In some instances, adjacent pairs of substituents 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 adjacent to each other on the same ring, or can be adjacent to each other on two rings with the two nearest available substitutable positions, such as the 2- and 2'-positions in biphenyl and the 1- and 8-positions in naphthalene, as long as a stable fused ring system can be formed.

[0053] B. Compounds of the Present Disclosure In one aspect, the present disclosure provides a method for producing a method of manufacturing a semiconductor device comprising: [ka] Ligand L A wherein ring A is independently a 5- to 10-membered heterocycle; X 1 ~X 6 are each independently C or N; K 3 is a direct bond, O, or S; the maximum number of N atoms bonded to each other in a ring is 2; R A , R B , and R C each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R, R A , R B , R C are each independently a substituent selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and the ligand L A is complexed with a metal M through two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can be coordinated to other ligands; the ligand L A can combine with other ligands to form tridentate, tetradentate, pentadentate, hexadentate, or heptadentate ligands; any two adjacent R A , R B , R C , or R 1, wherein the compound is: [ka] can be linked or fused to form a ring, provided that the ring does not contain either of the structures shown in

[0054] In some embodiments, R, R A , and R B can each independently be 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.

[0055] In some embodiments, X 1 ~X 3 can each be C. In some embodiments, X 4 ~X 6 can each be C. In some embodiments, X 1 ~X 6 can each be C.

[0056] In some embodiments, two adjacent R A The substituents can be attached to form a fused ring to ring A. In some embodiments, when ring A is a 7-, 8-, 9-, or 10-membered ring, four adjacent R A The substituents can be linked to form two fused rings to ring A. In some embodiments, when ring A is an 8-, 9-, or 10-membered ring, a total of six adjacent R AThe substituents can be bonded to form three separate rings, all fused to ring A. In some embodiments, the fused rings can each independently be a 5- or 6-membered aromatic ring. In some embodiments, the fused rings can each independently be benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole. In some embodiments, the fused rings can each independently be benzene or imidazole. In some embodiments, the fused rings can all be benzene.

[0057] In some embodiments, one R substituent and one R of Formula I B The substituents can be linked to form a ring. In some embodiments, one R substituent and one R of Formula I can be linked to form a ring. A The substituents can be linked to form a ring. In some embodiments, one R of Formula II C Substituent and one R B The substituents can be linked to form a ring. In some embodiments, one R of Formula II C Substituent and one R A The substituents can be linked to form a ring. In some embodiments, two adjacent R B The substituents can be linked to form a fused ring. In some embodiments, two adjacent R C The substituents can be joined to form a fused ring.

[0058] In some embodiments, the ligand L A can be selected from the group consisting of: [ka] JPEG0007799418000006.jpg5585In the formula, ring A1 is independently a 5- to 10-membered heterocycle; rings A2, A3, A4, A5, B2, and B3 are each independently a 5- or 6-membered carbocycle or heterocycle; and ring B1 is independently a 5-, 6-, or 7-membered carbocycle or heterocycle.

[0059] In some embodiments, the ligand L A can be selected from the group consisting of: [ka] JPEG0007799418000008.jpg110150 wherein each Q is independently C or N; each W is independently BR, BRR, NR, PR, O, S, Se, C═O, S═O, SO2, C═CRR′, CRR′, SiRR′, or GeRR′, where R and R′ are each independently hydrogen or a substituent selected from the group consisting of the general substituents described herein.

[0060] In some embodiments, the ligand L A is the following: [ka] In some embodiments, the ligand L A is the following: [ka] wherein R A1 , R A2 , and R A3 each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R A1 , R A2 , and R A3 are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein. In some embodiments, the ligand L A teeth, [ka] In some of the above embodiments, X 1 ~X 6 may each independently be C. In some of the above embodiments, X 1 ~X 6 One of X can be N. In some of the above embodiments, 1 ~X 3 One of X can be N. In some of the above embodiments, 3 ~X 6 One of R can be N. In some of the above embodiments, A1 , R A2 , R A3 , and R C In some of the above embodiments, one of R can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. A1 In some of the above embodiments, one of R can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. A2 In some of the above embodiments, one of R can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. A3 In some of the above embodiments, one of R can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. C In some of the above embodiments, one of R can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. A1 , R A2 , and R A3 One of R can be t-butyl or phenyl. In some of the above embodiments, R A1 One of R can be t-butyl, or substituted or unsubstituted phenyl. In some of the above embodiments, RA2 One of R can be t-butyl, or substituted or unsubstituted phenyl. In some of the above embodiments, R A3 One of R can be t-butyl, or substituted or unsubstituted phenyl. In some of the above embodiments, R C One of R can be t-butyl, or substituted or unsubstituted phenyl. In some of the above embodiments, R A1 In some of the above embodiments, one of R A2 In some of the above embodiments, one of R A3 In some of the above embodiments, one of R can be a fully deuterated phenyl. A1 are independently deuterium. In some of the above embodiments, each R A2 are independently deuterium. In some of the above embodiments, each R A3 are independently deuterium. In some of the above embodiments, each R C are independently deuterium. In some of the above embodiments, R A1 , R A2 , R A3 , and R C are each independently deuterium. In some of the above embodiments, R A1 , R A2 , R A3 , and R C are each independently H. In some of the above embodiments, two R B can be linked to form a 5-membered or 6-membered ring. In some of the above embodiments, one R C and one R B and can be linked to form a ring.

[0061] In some embodiments, the ligand L A L A 1-(Rs)(Rt)(Ru), L A 2-(Rs)(Rt)(Ru), LA 3-(Rs)(Rt)(Ru), L A 4-(Rs)(Rt)(Ru), L A 5-(Rs)(Rt)(Ru), L A 6-(Rs)(Rt)(Ru), L A 7-(Rs)(Rt)(Ru), L A 8-(Rs)(Rt)(Ru), L A 9-(Rs)(Rt)(Ru), L A 10-(Rs)(Rt)(Ru), L A 11-(Rs)(Rt)(Ru), L A 12-(Rs)(Rt)(Ru), L A 13-(Rs)(Rt)(Ru), L A 14-(Rs)(Rt)(Ru), L A 15-(Rs)(Rt)(Ru), L A 16-(Rs)(Rt)(Ru), L A 17-(Rs)(Rt)(Ru), L A 18-(Rs)(Rt)(Ru), L A 19-(Rs)(Rt)(Ru), L A 20-(Rs)(Rt)(Ru), L A 21-(Rs)(Rt)(Ru), L A 22-(Rs)(Rt)(Ru), L A 23-(Rs)(Rt)(Ru), L A 24-(Rs)(Rt)(Ru), L A 25-(Rs)(Rt)(Ru), L A 26-(Rs)(Rt)(Ru), L A 27-(Rs)(Rt)(Ru), L A 28-(Rs)(Rt)(Ru), L A 29-(Rs)(Rt)(Ru), L A 30-(Rs)(Rt)(Ru), L A 31-(Rs)(Rt)(Ru), and L A 32-(Rs)(Rt)(Ru), wherein s, t, and u are each independently an integer from 1 to 87, and wherein: [ka] JPEG0007799418000013.jpg205151JPEG0007799418000014.jpg201149JPEG0007799418000015.jpg121149In the formula, R1 to R87 have the following structure: [ka] JPEG0007799418000017.jpg217158JPEG0007799418000018.jpg153156

[0062] In some embodiments, the compound has the formula M(L A ) p (L B ) q (L C ) r wherein L B and L C are each a bidentate ligand; p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M.

[0063] In some embodiments, the compound is Ir(L A )3, Ir(L A )(L B )2, Ir(L A )2(L B ), Ir(L A )2(L C ), and Ir(L A )(L B )(L C ), wherein L A , L B , and L C are different from each other.

[0064] In some embodiments, the compound has the formula Pt(L A )(L B ), wherein L A and L Bmay be the same or different. In some embodiments, L A and L B can be linked to form a tetradentate ligand.

[0065] In some embodiments, L B and L C can each independently be selected from the group consisting of: [ka] During the ceremony, T is selected from the group consisting of B, Al, Ga, and In; Y 1 ~Y 13 are each independently selected from the group consisting of carbon and nitrogen; Y' is BR e , N.R. e , PR e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of: R e and R f can be fused or linked to form a ring; Each R a , R b , R c , and R d independently represent zero, mono, or up to the maximum number of possible substitutions for its associated ring; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e , and R fare each independently a substituent selected from the group consisting of hydrogen or deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and the general substituents described herein; Any two adjacent R a , R b , R c , R d , R e , and R f can be fused or linked to form a ring or to form a multidentate ligand.

[0066] In some embodiments, L B and L C can each independently be selected from the group consisting of: [ka] JPEG0007799418000021.jpg210158JPEG0007799418000022.jpg116125 R a ', R b ', and R c each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R a1 , R b1 , R c1 , R a , R b , R c , R N , R a ', R b ', and R ceach ' is independently a substituent selected from the group consisting of hydrogen or deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; Any two adjacent R a ', R b ', and R c The ' may be fused or linked to form a ring or to form a multidentate ligand.

[0067] In some embodiments, the compound is Ir(L A )3, Ir(L A )(L Bk )2, Ir(L A )(L BBn )2, Ir(L A )2(L Bk ), Ir(L A )2(L BBn ), Ir(L A )2(L Cj-I ), and Ir(L A )2(L Cj-II ) may be selected from the group consisting of In the formula, L A is a ligand described herein; k is an integer from 1 to 324, and each L Bk is defined in Listing 2 below. [ka] JPEG0007799418000024.jpg220155JPEG0007799418000025.jpg217158JPEG000779941800002 6.jpg221156JPEG0007799418000027.jpg212157JPEG0007799418000028.jpg224157JPEG00077 99418000029.jpg202156JPEG0007799418000030.jpg236155JPEG0007799418000031.jpg233156JPEG0007799418000032.jpg236157JPEG0007799418000033.jpg49144In the formula, n is an integer from 1 to 180, and each L BBn is defined in Listing 3 below. [ka] JPEG0007799418000035.jpg201158JPEG0007799418000036.jpg202157JPEG0007799418000037.jpg233157JPEG000779941800 0038.jpg205156JPEG0007799418000039.jpg223156JPEG0007799418000040.jpg210157JPEG0007799418000041.jpg4366In the formula, each L Cj-I is the expression: [ka] Each L Cj-II is the expression: [ka] and having a structure based on In the formula, L Cj-I and L Cj-II Each L in Cj About R 201 and R 202 are each independently defined in List 4 below. [ka] JPEG0007799418000045.jpg234156JPEG0007799418000046.jpg234155JPEG000779941800 0047.jpg233156JPEG0007799418000048.jpg234156JPEG0007799418000049.jpg233156JP EG0007799418000050.jpg234156JPEG0007799418000051.jpg233156JPEG00077994180000 52.jpg233155JPEG0007799418000053.jpg233155JPEG0007799418000054.jpg194156In formula, R D1 ~R D246 has the following structure: [ka] JPEG0007799418000056.jpg223156JPEG0007799418000057.jpg233156JPEG0007799418000058.jpg225156JPEG0007799418000059.jpg113158

[0068] In some embodiments, the compound has the formula Ir(L A )(L Bk )2, Ir(L A )(L BBn )2, Ir(L A )2(L Bk ), or Ir(L A )2(L BBn ), and the compound can have L Bk or L BBn As a ligand, it consists of only one of the following structures: B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B130 , LB132 and L B134 and L B136 and L B138 and L B140 and L B142 and L B144 and L B156 and L B158 and L B160 and L B162 and L B164 and L B168 and L B172 and L B175 and L B204 and L B206 and L B214 and L B216 and L B218 and L B220 and L B222 and L B231 and L B233 and L B235 and L B237 and L B240 and L B242 and L B244 and L B246 and L B248 and L B250 and L B252 and L B254 and L B256 and L B258 and L B260 and L B262 and L B264 and L B265 and L B266 and L B267 and L B268 and L B269 and L B270 and L BB1 and L BB2 and L BB3 and L BB4 and L BB5 and L BB6 and L BB7 and L BB8 and L BB9 and L BB10 and L BB11 and L BB2 and L BB13 and L BB14 and L BB15 and L BB16 and L BB17 and L BB18 and L BB20 and L BB22 and L BB24 and 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 BB116 , L BB117 , L BB118 , L BB119 , L BB121 , L BB122 , and L BB123 .

[0069] In some embodiments, the compound has the formula Ir(L A )(L Bk )2, Ir(L A )(L BBn )2, Ir(L A )2(L Bk ), or Ir(L A )2(L BBn ), and the compound can have L Bk or L BBn As a ligand, it consists of only one of the following structures: B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B126 , L B128 , L B132 , L B136 , L B138 , L B142 , L B156 , L B162 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B231 , L B233 , L B237 , L B264 , L B265 , LB266 , L B267 , L B268 , L B269 , L B270 , 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 BB107 , L BB113 , L BB115 , L BB116 , and L BB121 .

[0070] In some embodiments, the compound is Ir(L A )2(L Cj-I ) or Ir(L A )2(L Cj-II ), and the ligand L Cj-I and L Cj-II and the compounds are represented by their corresponding R 201 and R 202 is defined as one of the following structures: Cj-I and L Cj-II Contains only ligands: R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D18 , R D20 , R D22 , R D37 , R D40 , R D41 , R D42 , R D43 , R D48 , R D49 , R D50 , R D54 , R D55 , R D58 , R D59, R D78 , R D79 , R D81 , R D87 , R D88 , R D89 , R D93 , R D116 , R D117 , R D118 , R D119 , R D120 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D147 , R D149 , R D151 , R D154 , R D155 , R D161 , R D175 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 .

[0071] In some embodiments, the compound has the formula Ir(L A )2(L Cj-I ) or Ir(L A )2(L Cj-II ), and the ligand L Cj-I and L Cj-II and the compounds are represented by their corresponding R 201 and R 202 is defined as one of the following structures: Cj-I and L Cj-II Contains only ligands: R D1 , R D3 , RD4 , R D5 , R D9 , R D10 , R D17 , R D22 , R D43 , R D50 , R D78 , R D116 , R D118 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D149 , R D151 , R D154 , R D155 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 .

[0072] In some embodiments, the compound has the formula Ir(L A )2(L Cj-I ), and the compound can have L Cj-I As a ligand, it consists of only one of the following structures: [ka] JPEG0007799418000061.jpg27146

[0073] In some embodiments, the compound can be selected from the group consisting of: [ka]

[0074] In some embodiments, the compound can have the following structure: [ka] During the ceremony, M 1 is Pd or Pt; Moieties C and D are each independently a monocyclic or polycyclic structure containing 5- and / or 6-membered carbocyclic or heterocyclic rings; Z 1 and Z 2 are each independently C or N; K 1 , K. 2 , and K 3 are each independently selected from a direct bond, O, and S; K 1 , K. 2 , or K 3 at least two of are direct bonds; L 1 , L 2 , and L 3 are each independently selected from the group consisting of a direct bond, BR, BRR, NR, PR, O, S, Se, C═O, S═O, SO, C═CRR′, CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, and combinations thereof; 1 and L 2 At least one of the following is present; n1, n2, and n3 are each 0 or 1, and n1+n2+n3=2 or 3; X 7 ~X 9 are each independently C or N; R C and R D each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R C and R Dare each 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; Any two adjacent R A , R B , R C , R D , or R 1 can be bonded or fused to each other to form a chemically feasible ring; and X 1 ~X 6 , R A , R B and ring A are both defined as above.

[0075] In some embodiments, moieties C and D can both be six-membered aromatic rings. In some embodiments, moiety C can be a five- or six-membered heterocycle.

[0076] In some embodiments, Z 2 is N and Z 1 is C. In some embodiments, Z 2 can be C, Z 1 can be N.

[0077] In some embodiments, L 1 can be O, SiRR′, or CRR′. In some embodiments, L 2 can be a direct bond. In some embodiments, L 2 can be NR.

[0078] In some embodiments, K 1 , K. 2 , and K 3 Each of K can be a direct bond. 1 , K. 2 , or K 3Any of K can be O. In some embodiments, K 1 or K 2 Any of K can be O. In some embodiments, K 3 can be O.

[0079] In some embodiments, X 7 ~X 9 can all be C.

[0080] In some embodiments, the compound can have the following structure: [ka] In the formula, Z 3 is C or N; the remaining variables are as defined above; any two adjacent R A , R B , R C , R D , or R 1 can be bonded to or fused with each other to form a ring.

[0081] In some embodiments of Formula V or Formula VI, R, R A , and R B can each independently be 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.

[0082] In some embodiments, X 1 ~X 3 can each be C. In some embodiments, X 4 ~X 6 can each be C. In some embodiments, X 1 ~X 6 can each be C.

[0083] In some embodiments, two adjacent R A The substituents can be attached to form a fused ring to ring A. In some embodiments, when ring A is a 7-, 8-, 9-, or 10-membered ring, two additional adjacent R A Substituents can be attached to form additional fused rings to ring A. In some embodiments, a total of six adjacent R A The substituents can be bonded to form three separate rings, all fused to ring A. In some embodiments, all fused rings can be 5- or 6-membered aromatic rings. In some embodiments, the fused rings can each independently be benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole. In some embodiments, all fused rings can each be benzene.

[0084] In some embodiments, one R substituent and one R of Formula V B The substituents can be linked to form a ring. In some embodiments, one R substituent and one R of Formula V A The substituents can be linked to form a ring. In some embodiments, one R of Formula VI C Substituent and one R B The substituents can be linked to form a ring. In some embodiments, one R of Formula VI C Substituent and one R A The substituents can be linked to form a ring. In some embodiments, two adjacent R B The substituents can be linked to form a fused ring. In some embodiments, two adjacent R C The substituents can be joined to form a fused ring.

[0085] In some embodiments, ring C and ring D can each independently be benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole.

[0086] In some embodiments, the compound can be selected from the group defined in List 5 below. [ka] JPEG0007799418000066.jpg196157JPEG0007799418000067.jpg145154In formula, R x and R y are each selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; R G are each 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; X 1 ~X 6 , R1, R A , R B , R C , R E , R F , L 1 and ring A are all the same as defined above.

[0087] In some embodiments, the compound can have the following structure: [ka] In the formula, L A’ L A’ 1-(Rs)(Rt)(Ru), L A’ 2-(Rs)(Rt)(Ru), L A’ 3-(Rs)(Rt)(Ru), L A’4-(Rs)(Rt)(Ru), L A’ 5-(Rs)(Rt)(Ru), L A’ 6-(Rs)(Rt)(Ru), L A’ 7-(Rs)(Rt)(Ru), L A’ 8-(Rs)(Rt)(Ru), and L A’ 9-(Rs)(Rt)(Ru), wherein s, t, and u are each independently an integer from 1 to 87; [ka] JPEG0007799418000070.jpg168144In formula, L A’’ L A’’ 1-(Rs)(Rt)(Ru), L A’’ 2-(Rs)(Rt)(Ru), L A’’ 3-(Rs)(Rt)(Ru), L A’’ 4-(Rs)(Rt)(Ru), L A’’ 5-(Rs)(Rt)(Ru), L A’’ 6-(Rs)(Rt)(Ru), L A’’ 7-(Rs)(Rt)(Ru), L A’’ 8-(Rs)(Rt)(Ru), L A’’ 9-(Rs)(Rt)(Ru), L A’’ 10-(Rs)(Rt)(Ru), L A’’ 11-(Rs)(Rt)(Ru), L A’’ 12-(Rs)(Rt)(Ru), L A’’ 13-(Rs)(Rt)(Ru), L A’’ 14-(Rs)(Rt)(Ru), L A’’ 15-(Rs)(Rt)(Ru), L A’’ 16-(Rs)(Rt)(Ru), L A’’ 17-(Rs)(Rt)(Ru), L A’’ 18-(Rs)(Rt)(Ru), L A’’ 19-(Rs)(Rt)(Ru), L A’’ 20-(Rs)(Rt)(Ru), L A’’ 21-(Rs)(Rt)(Ru), L A’’ 22-(Rs)(Rt)(Ru), L A’’23-(Rs)(Rt)(Ru), and L A’’ 24-(Rs)(Rt)(Ru), wherein s, t, and u are each independently an integer from 1 to 87; [ka] JPEG0007799418000072.jpg225160JPEG0007799418000073.jpg148160In the formula, the ligand L Y L Y 1-(Rs)(Rt)(Ru), L Y 2-(Rs)(Rt)(Ru), L Y 3-(Rs)(Rt)(Ru), L Y 4-(Rs)(Rt)(Ru), L Y 5-(Rs)(Rt)(Ru), L Y 6-(Rs)(Rt)(Ru), L Y 7-(Rs)(Rt)(Ru), L Y 8-(Rs)(Rt)(Ru), L Y 9-(Rs)(Rt)(Ru), L Y 10-(Rs)(Rt)(Ru), L Y 11-(Rs)(Rt)(Ru), L Y 12-(Rs)(Rt)(Ru), L Y 13-(Rs)(Rt)(Ru), L Y 14-(Rs)(Rt)(Ru), L Y 15-(Rs)(Rt)(Ru), L Y 16-(Rs)(Rt)(Ru), L Y 17-(Rs)(Rt)(Ru), L Y 18-(Rs)(Rt)(Ru), L Y 19-(Rs)(Rt)(Ru), L Y 20-(Rs)(Rt)(Ru), L Y 21-(Rs)(Rt)(Ru), L Y 22-(Rs)(Rt)(Ru), L Y 23-(Rs)(Rt)(Ru), L Y 24-(Rs)(Rt)(Ru), L Y 25-(Rs)(Rt)(Ru), L Y26-(Rs)(Rt)(Ru), L Y 27-(Rs)(Rt)(Ru), L Y 28-(Rs)(Rt)(Ru), L Y 29-(Rs)(Rt)(Ru), L Y 30-(Rs)(Rt)(Ru), L Y 31-(Rs)(Rt)(Ru), L Y 32-(Rs)(Rt)(Ru), L Y 33-(Rs)(Rt)(Ru), wherein s, t, and u are each independently an integer from 1 to 87; [ka] JPEG0007799418000075.jpg222160JPEG0007799418000076.jpg194160JPEG0007799418000077.jpg39160In the formula, R1 to R87 have the following structures. [ka] JPEG0007799418000079.jpg203156JPEG0007799418000080.jpg82156

[0088] In some embodiments, the compound can be selected from the group defined in List 9 below. [ka] JPEG0007799418000082.jpg204140JPEG0007799418000083.jpg203144JPEG0007799418000084.jpg236153JPEG000 7799418000085.jpg232147JPEG0007799418000086.jpg211146JPEG0007799418000087.jpg214154JPEG00077994180 00088.jpg189141JPEG0007799418000089.jpg233144JPEG0007799418000090.jpg225156JPEG0007799418000091.j pg213158JPEG0007799418000092.jpg201116JPEG0007799418000093.jpg215153JPEG0007799418000094.jpg130123

[0089] In some embodiments, the compound can be selected from the group consisting of the following structures: [ka] JPEG0007799418000096.jpg183158JPEG0007799418000097.jpg184157JPEG0007799418 000098.jpg215157JPEG0007799418000099.jpg171159JPEG0007799418000100.jpg7362

[0090] In some embodiments, the ligand L of Formula I or Formula II described herein Acan be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percentage of available hydrogen atoms (e.g., hydrogen, deuterium, or halogen positions) that are replaced by deuterium atoms.

[0092] C. OLEDs and Devices of the Present Disclosure In another aspect, the present disclosure also provides an OLED device that includes a first organic layer containing a compound disclosed in the Compounds section of this disclosure.

[0093] In some embodiments, the organic layer comprises: [ka] Ligand L A wherein ring A is independently a 5- to 10-membered heterocycle; 1 ~X 6 are each independently C or N; K 3 is a direct bond, O, or S; the maximum number of N atoms bonded to each other in a ring is 2; R A , R B , and R C each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R, R A , R B , R C are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein, and the ligand L A is complexed with a metal M through two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can be coordinated to other ligands; the ligand LA can combine with other ligands to form tridentate, tetradentate, pentadentate, hexadentate, or heptadentate ligands; any two adjacent R A , R B , R C , or R 1, wherein the compound is: [ka] can be linked or fused to form a ring, provided that the ring does not contain either of the structures shown in

[0094] In some embodiments, the organic layer can be an emissive layer, and the compounds described herein can be an emissive or non-emissive dopant.

[0095] In some embodiments, the organic layer can further include a host, the host including a triphenylene containing benzo-fused thiophene or a benzo-fused furan, and any substituents in the host can independently be selected from the group consisting of C n H 2n+1 , O.C. n H 2n+1 , OAr1, N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CC n H 2n+1 , Ar1, Ar1-Ar2, C n H 2n -Ar1 is a non-fused substituent selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof, or can be unsubstituted, and n is 1 to 10. Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

[0096] In some embodiments, the organic layer can further include a host, wherein the host comprises 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-boranaphtho[3,2,1-de]anthracene).

[0097] In some embodiments, the host may be selected from the group selected from the group consisting of: [ka] JPEG0007799418000104.jpg213156JPEG0007799418000105.jpg155156

[0098] In some embodiments, the organic layer can further comprise a host, wherein the host comprises a metal complex.

[0099] 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 a combination thereof.

[0100] In yet another embodiment, the OLED of the present disclosure can also include a light-emitting region comprising a compound disclosed in the Compounds section of this disclosure.

[0101] In some embodiments, the light emitting region comprises: [ka] Ligand LA wherein ring A is independently a 5- to 10-membered heterocycle; 1 ~X 6 are each independently C or N; K 3 is a direct bond, O, or S; the maximum number of N atoms bonded to each other in a ring is 2; R A , R B , and R C each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R, R A , R B , R C are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein, and the ligand L A is complexed with a metal M via two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can be coordinated to other ligands; the ligand L A can combine with other ligands to form tridentate, tetradentate, pentadentate, hexadentate, or heptadentate ligands; any two adjacent R A , R B , R C , or R 1, wherein the compound is: [ka] can be linked or fused to form a ring, provided that the ring does not contain either of the structures shown in

[0102] In some embodiments, at least one of the anode, cathode, or additional layers disposed on the organic light-emitting layer functions as an enhancement layer. The enhancement layer includes a plasmonic material that nonradiatively couples to the emitter material and exhibits a surface plasmon resonance that transfers excited-state energy from the emitter material to a nonradiative mode of surface plasmon polaritons. The enhancement layer is disposed within a threshold distance from the organic light-emitting layer, and the emitter material has a total nonradiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer, and at the threshold distance, the total nonradiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer opposite the organic light-emitting layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the enhancement layer from the light-emitting layer, but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. If the energy is scattered into a non-free-space mode of the OLED, other outcoupling schemes can be incorporated to extract the energy into free space. In some embodiments, one or more intervening layers can be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers can be dielectric materials, including organic, inorganic, perovskite, and oxide, and can include stacks and / or mixtures of these materials.

[0103] Enhancement layers alter the effective properties of the medium in which the emitter material resides, resulting in any or all of the following: a reduction in the emission rate; a change in the emission line shape; a change in the emission intensity with angle; a change in the stability of the emitter material; a change in the efficiency of the OLED; and a reduction in the efficiency roll-off of the OLED device. Placing an enhancement layer on the cathode side, the anode side, or both can result in an OLED device that utilizes any of the above-described effects. In addition to the specific functional layers shown in the various OLED examples described and illustrated herein, OLEDs according to the present disclosure can include any of the other functional layers frequently found in OLEDs.

[0104] The enhancement layer can be composed of a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material whose real part of its permittivity crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material includes at least one metal. In such embodiments, the metal can include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials such that the medium as a whole behaves differently from the sum of its parts. In particular, an optically active metamaterial is defined as a material that has both a negative permittivity and a negative magnetic permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium in which the permittivity or permeability has different signs in different spatial directions. Optically active metamaterials and hyperbolic metamaterials are distinct from many other photonic structures, such as distributed Bragg reflectors ("DBRs"), in that they are media that appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology understood by those skilled in the art, the dielectric constant of a metamaterial in the direction of propagation can be described by an effective medium approximation. Plasmonic materials and metamaterials offer a way to control the propagation of light and can improve OLED performance in a variety of ways.

[0105] In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features or periodically, quasi-periodically, or randomly arranged sub-wavelength-sized features. In some embodiments, the wavelength-sized features and sub-wavelength-sized features have sharp edges.

[0106] In some embodiments, the outcoupling layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features or periodically, quasi-periodically, or randomly arranged subwavelength-sized features. In some embodiments, the outcoupling layer can be composed of nanoparticles, and in other embodiments, the outcoupling layer is composed of nanoparticles disposed on a material. In these embodiments, outcoupling can be tunable by at least one of varying the size of the nanoparticles, varying the shape of the nanoparticles, varying the material of the nanoparticles, adjusting the thickness of the material, varying the refractive index of the material or the refractive index of an additional layer disposed on the nanoparticles, varying the thickness of an enhancement layer, and / or varying the material of the enhancement layer. The nanoparticles of the device can be formed from at least one of a metal, a dielectric material, a semiconductor material, an alloy of a metal, a mixture of dielectric materials, a stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, the metal being selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. The nanoparticles can have additional layers disposed thereon. In some embodiments, the polarization of the emitted light can be adjusted using the outcoupling layer. By varying the dimensions and periodicity of the outcoupling layer, the type of polarization that is preferentially outcoupled to air can be selected. In some embodiments, the outcoupling layer also functions as an electrode for the device.

[0107] 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 this disclosure.

[0108] In some embodiments, the consumer product includes an organic light emitting device (OLED) having an anode, a cathode, and an organic layer between the anode and the cathode, the organic layer comprising: [ka] Ligand L A wherein ring A is independently a 5- to 10-membered heterocycle; 1 ~X 6 are each independently C or N; K 3 is a direct bond, O, or S; the maximum number of N atoms bonded to each other in a ring is 2; R A , R B , and R C each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R, R A , R B , R C are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein, and the ligand L A is complexed with a metal M via two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can be coordinated to other ligands; the ligand L A can combine with other ligands to form tridentate, tetradentate, pentadentate, hexadentate, or heptadentate ligands; any two adjacent R A , R B , R C , or R 1, wherein the compound is: [ka] can be linked or fused to form a ring, provided that the ring does not contain either of the structures shown in

[0109] 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 in 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.

[0110] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons migrate to the oppositely charged electrode, respectively. When an electron and hole localize on the same molecule, an "exciton," a localized electron-hole pair with an excited energy state, is formed. 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, can also occur but are generally considered undesirable.

[0111] 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.

[0112] 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 in a time frame of less than 10 nanoseconds.

[0113] 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, No. 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, No. 3, 4-6 (1999) ("Baldo-II"), 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.

[0114] FIG. 1 shows an organic light-emitting device 100. The drawing is not necessarily to scale. Device 100 may include a substrate 110, an anode 115, a hole-injection layer 120, a hole-transport layer 125, an electron-blocking layer 130, an emissive layer 135, a hole-blocking layer 140, an electron-transport layer 145, an electron-injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in further detail in U.S. Pat. No. 7,279,704, cols. 6-10, which are incorporated by reference.

[0115] Further examples are available for each of these layers. 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-transporting layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron-transporting layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, 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 entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0116] 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 can be omitted from the structure of device 100.

[0117] The simple layer structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present disclosure can 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 various layers as including a single material, it is understood that combinations of materials, such as a mixture of a host and a dopant, or more generally, a mixture, 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.

[0118] Structures and materials not specifically described may also be used, such as OLEDs (PLEDs) composed of polymeric materials, such as those disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As a further example, an OLED having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from the simple layered structures illustrated in FIGS. 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as the mesa structure described in U.S. Pat. No. 6,091,195 to Forrest et al. and / or the recessed structure described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0119] Unless otherwise specified, any of the layers of the various embodiments can 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 entireties; inkjet deposition; organic vapor phase deposition (OVPD), such as that 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 that 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 performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include patterning through a mask, such as those described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, deposition via cold welding, and patterning associated with some deposition methods, such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to be compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, preferably containing at least three 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 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution processability than those with symmetric structures, because asymmetric materials may be less prone to recrystallization. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0120] 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. The barrier layer may be deposited over, under, or adjacent to the substrate, the electrode, or 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 and 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.

[0121] 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), and the like, which can be utilized by end-user product manufacturers. Such electronic component modules can optionally include drive 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. Consumer products are disclosed 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, head-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, light therapy devices, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices fabricated according to the present disclosure. Many of the devices are intended for use within a temperature range comfortable to humans, such as 18°C ​​to 30°C, and more preferably room temperature (20-25°C), but can also be used outside this temperature range, e.g., between -40°C and +80°C.

[0122] Further details regarding OLEDs and the definitions set forth above can be found in US Pat. No. 7,279,704, which is incorporated by reference in its entirety.

[0123] 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.

[0124] 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 translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

[0125] 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.

[0126] 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 (TADF) (also known as E-type delayed fluorescence; see, e.g., U.S. Application No. 15 / 700,352, 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 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). When more than one ligand is present 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 combine with other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Thus, when the coordinating ligands are bonded to one another, in some embodiments, all of the ligands can be identical, while in some other embodiments, at least one of the bonded ligands can be different from the other ligands.

[0127] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, where one or more layers in the OLED contain 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 can emit energy or further transfer energy to the 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.

[0128] According to another aspect, compositions comprising the compounds described herein are also disclosed.

[0129] The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronic component modules, and lighting panels. The organic layer can be an emissive layer, and in some embodiments, the compound can be an emissive dopant, while in other embodiments, the compound can be a non-emissive dopant.

[0130] In yet another aspect of the present disclosure, there is provided a composition comprising the novel compounds disclosed herein. The composition may also comprise 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.

[0131] The present disclosure encompasses any chemical structure comprising 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.

[0132] D. Combinations of Compounds of the Present Disclosure with Other Materials 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 readily consult the literature to identify other materials that may be useful in combination.

[0133] a) Conductive (electrically conductive) dopants: The charge transport layer is doped with a conductive dopant to significantly change the density of charge carriers and thereby its conductivity. The conductivity can be increased by generating 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 n-type conductive dopants are used in the electron transport layer.

[0134] 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]

[0135] b) HIL / HTL: The hole injection / transport material used in the present disclosure is not particularly limited, and any compound may be used as long as it is a compound typically used as a hole injection / transport material. Examples of such 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 x p-type semiconducting organic compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes, and crosslinkable compounds.

[0136] Examples of HIL / HTL can be found in paragraphs

[0111] to

[0117] of Universal Display Corporation's U.S. Patent Application Publication No. 2020 / 0,295,281 A1, the contents of which paragraphs and the entire disclosure are incorporated herein by reference.

[0137] c) EBL: An electron blocking layer (EBL) 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 a desired region 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.

[0138] d) Host: 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 can be used as long as the triplet energy of the host is higher than that of the dopant. Any host material can be used with any dopant as long as the triplet criterion is met.

[0139] Examples of hosts can be found in paragraphs

[0119] to

[0125] of Universal Display Corporation's U.S. Patent Application Publication No. 2020 / 0,295,281 A1, the contents of which paragraphs and the entire disclosure are incorporated herein by reference.

[0140] e) Additional luminaries: One or more additional emitter dopants can be used together with the compound of the present disclosure.The example of the additional emitter dopant is 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 light emission through phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes. Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified in paragraphs

[0126] -

[0127] of Universal Display Corporation's U.S. Patent Application Publication No. 2020 / 0,295,281 A1, the contents of which paragraphs and the entire disclosure are incorporated herein by reference.

[0141] f) HBL: A hole-blocking layer (HBL) can be used to reduce the number of holes and / or excitons that escape from 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 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 from the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the HBL interface.

[0142] 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.

[0143] 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.

[0144] g)ETL: 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 typically used to transport electrons may be used.

[0145] 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 3has 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.

[0146] In another embodiment, the metal complex used in the ETL comprises, but is not limited to, the following general formula: [ka] where (ON) or (NN) is a bidentate ligand with the metal coordinated to 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. Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified in paragraphs

[0131] to

[0134] of Universal Display Corporation's U.S. Patent Application Publication No. 2020 / 0,295,281 A1, the contents of which paragraphs and the entire disclosure are incorporated herein by reference.

[0147] h) Charge Generation Layer (CGL) In tandem or stacked OLEDs, the CGL plays a key role in performance and consists of an n-doped layer and a p-doped layer for electron and hole injection, respectively. Electrons and holes are supplied from the CGL and the electrodes. Consumed electrons and holes in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively, until the bipolar current gradually reaches a steady state. Typical CGL materials contain n-type and p-type conductivity 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. The minimum amount of hydrogen in a deuterated compound is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, any specifically recited substituent, such as, but not limited to, methyl, phenyl, pyridyl, etc., can be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents, such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc., can be undeuterated, partially deuterated, and fully deuterated versions thereof.

[0149] It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. Thus, the present 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 various theories as to why the invention works are not intended to be limiting.

[0150] Experimental Section

[0151] Synthesis of luminescent material 1

[0152] Synthesis of 2-(2-((2-nitrophenyl)amino)phenyl)propan-2-ol [ka] 1-Iodo-2-nitrobenzene (3.75 g, 15.1 mmol), 2-(2-aminophenyl)propan-2-ol (2.28 g, 15.1 mmol), cesium carbonate (7.37 g, 22.6 mmol), Pd2dba3 (0.28 g, 0.30 mmol), and SPhos (0.49 g, 1.2 mmol) were added to a flask containing toluene (120 mL) and refluxed overnight. The reaction was cooled to room temperature (RT) and filtered through Celite. The residue was purified by column chromatography (10–20% ethyl acetate in heptane) to afford the desired product as an orange-yellow solid (95% yield).

[0153] Synthesis of 9,9-dimethyl-4-nitro-9,10-dihydroacridine [ka] 2-(2-((2-nitrophenyl)amino)phenyl)propan-2-ol (2.0 g, 7.3 mmol) and phosphoric acid (0.72 g, 7.34 mmol) were added to a flask and heated at 50° C. for 12 hours. The reaction was cooled and poured into ice water. A red solid was collected by filtration (96% yield).

[0154] Synthesis of 9,9-dimethyl-9,10-dihydroacridin-4-amine [ka] 9,9-Dimethyl-4-nitro-9,10-dihydroacridine (8.0 g, 31.4 mmol) and palladium on carbon (2.0 g) were added to a flask containing ethyl acetate and stirred overnight. The reaction was filtered and evaporated to give the desired compound (86% yield).

[0155] Synthesis of 6,6-dimethyl-6H-2l2,11l4-imidazo[5,4,3-de]acridine: [ka]

[0156] 9,9-Dimethyl-9,10-dihydroacridin-4-amine (12.0 g, 53.5 mmol), triethoxymethane (7.93 g, 53.5 mmol), and para-toluenesulfonic acid (1.02 g, 5.35 mmol) were added to a flask equipped with a stir bar and stirred overnight at 80 °C. The reaction was cooled to rt, diluted with ethyl acetate, and washed with aqueous sodium bicarbonate. The organic layers were combined, dried, and evaporated, and the residue was purified by column chromatography (2% MeOH in DCM) to give an oil (89% yield).

[0157] Synthesis of 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-6,6-dimethyl-2,6-dihydroimidazo[4,5,1-de]acridin-11-ium tetrafluoroborate [ka] 6,6-Dimethyl-6H-212,1114-imidazo[5,4,3-de]acridine (156 mg, 0.666 mmol), (3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)(mesityl)iodonium tetrafluoroborate (531 mg, 0.732 mmol), and bis(((trifluoromethyl)sulfonyl)oxy)copper (24.08 mg, 0.067 mmol) were added to a 25 mL tube with a stir bar and cycled onto the line. Anhydrous DMF (6.658 mL) was added, and the reaction was heated to 120° C. overnight. The reaction was cooled to RT, and water was added to produce a white precipitate. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with saturated LiCl solution, dried over MgSO, filtered, and degassed. Isolation was achieved by column chromatography using 1:1 CHCN:DCM as eluent. Pure fractions were combined and evaporated to give the desired compound as a white solid (55% yield).

[0158] Synthesis of luminescent material 1 [ka] 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-6,6-dimethyl-2,6-dihydroimidazo[4,5,1-de]acridin-11-ium tetrafluoroborate (194 mg, 0.272 mmol) was added to a 25 mL flask equipped with a stir bar. Ortho-dichlorobenzene (5 mL) was added, followed by potassium bis(trimethylsilyl)amide (0.272 mL, 0.272 mmol) via syringe. (COD)PtCl2 (102 mg, 0.272 mmol) was added as a solid, and the reaction was heated to reflux. Thin-layer chromatography (TLC) in 1:1 Hep:DCM showed an emission spot at an rf of approximately 0.5. A color gradient was observed from the top of this spot to the bottom. The reaction was heated overnight. The reaction was cooled to RT and the solvent was evaporated off. The residue was purified by column chromatography to give the desired compound as a yellow solid (22% yield).

[0159] Synthesis of luminescent material 2 Synthesis of 5-iodo-1-phenyl-1H-imidazole [ka]

[0160] A dry 1000 mL reaction tube was charged with Cu(OTf) (3.15 g, 8.66 mmol, 5 mol%), cesium carbonate (85 g, 260 mmol), and 1-methylbenzimidazole (4.60 g, 34.7 mmol, 20 mol%). Hexafluoroisopropanol (700 mL) was added, and the mixture was stirred at rt for 30 min before adding (1H-imidazol-5-yl)(phenyl)-1-3-iodanyl acetate (57.5 g, 173 mmol, 1.0 equiv). The tube was capped, and the mixture was heated to 55 °C for 26 h. The solvent was removed, and the product was isolated by column chromatography eluting with hexane:EtOAc mixtures (100% hexane to 50% hexane / EtOAc) to give the desired product (40% yield).

[0161] Synthesis of 2,2-dimethyl-1-(1-phenyl-1H-imidazol-5-yl)propan-1-one: [ka] 5-Iodo-1-phenyl-1H-imidazole (0.320 g, 1.185 mmol, 1.0 equiv) and THF (4 mL) were added to a round-bottom flask. The solution was cooled to −78° C. over 30 minutes. Isopropylmagnesium chloride (1.03 mL, 1.303 mmol, 1.1 equiv) was added dropwise over 2 minutes to the stirred solution and stirred at room temperature for 3 hours. The reaction was cooled to −78° C. and pivaloyl chloride (0.290 mL, 2.37 mmol, 2.0 equiv) was added dropwise over 2 minutes. The reaction mixture was stirred at 23° C. overnight. The reaction was quenched with saturated NH4Cl, diluted with EtOAc, washed with saturated NaCl, DI water, and dried over Na2SO4. The crude material was purified by column chromatography (50% ethyl acetate:hexanes) to give the desired product (42% yield).

[0162] Synthesis of 3,3-dimethyl-2-(1-phenyl-1H-imidazol-5-yl)butan-2-ol: [ka] 2,2-Dimethyl-1-(1-phenyl-1H-imidazol-5-yl)propan-1-one (0.150 g, 0.657 mmol, 1 equiv.) and THF (3 mL) were added to a round-bottom flask. The mixture was cooled to −78° C. with stirring for 15 minutes. Methyllithium (1.00 mL, 1.64 mmol, 2.5 equiv.) was added dropwise to the solution. The reaction was allowed to stir at −78° C. for 1 hour and then warmed to room temperature for 4 hours. The reaction was quenched with saturated NH4Cl at 0° C., diluted with EtOAc, and washed with saturated NaCl, saturated brine, and DI water. The reaction was purified by column chromatography to give the desired product (65% EtOAc in hexanes) in 78% yield.

[0163] Synthesis of 4,4,5,5-tetramethyl-4,5-dihydroimidazo[1,5-a]quinoline: [ka]

[0164] 3,3-Dimethyl-2-(1-phenyl-1H-imidazol-5-yl)butan-2-ol (0.100 g, 0.409 mmol, 1 equiv) and DCM (6 mL) were added to a flask equipped with a stir bar. After the mixture was stirred at 0 °C for 30 minutes, aluminum trichloride (0.546 g, 4.09 mmol, 10 equiv) was added in one portion. The reaction was stirred at 0 °C for 1 hour and then warmed to room temperature for 5 hours. The reaction was cooled to 0 °C, quenched with saturated Na2CO3, diluted with ethyl acetate, and washed with brine and DI water. The reaction was purified by column chromatography (60% ethyl acetate in hexanes) to give the desired product (96% yield).

[0165] Synthesis of 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-4,4,5,5-tetramethyl-4,5-dihydro-2H-1014-imidazo[1,5-a]quinoline, tetrafluoroborate salt [ka] 4,4,5,5-Tetramethyl-4,5-dihydroimidazo[1,5-a]quinoline (0.40 g, 1.75 mmol), (3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)(mesityl)iodonium tetrafluoroborate (1.4 g, 1.933 mmol), and bis(((trifluoromethyl)sulfonyl)oxy)copper (0.064 g, 0.176 mmol) were added to a Schlenk tube equipped with a stir bar. Anhydrous DMF (6.658 mL) was added and the reaction was heated to 120° C. overnight. The reaction was cooled to RT and the solvent was evaporated. The residue was dissolved in a minimum amount of DCM, EtO was added, and the off-white solid was collected by filtration (97% yield).

[0166] Synthesis of luminescent material 2 [ka] 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-4,4,5,5-tetramethyl-4,5-dihydro-2H-imidazo[1,5-a]quinolin-10-ium tetrafluoroborate (100 mg, 0.142 mmol) and monosilver(I) monosilver(III) monoxide (16.44 mg, 0.071 mmol) were added to a 100 mL round-bottom flask equipped with a stir bar. 1,2-Dichloroethane (3 mL) was added and the reaction was stirred at RT overnight. The reaction solvent was evaporated to give a foam. This was reacted with a solution of (COD)PtCl2 (53.1 mg, 0.142 mmol) in ortho-dichlorobenzene (3.00 mL) under reflux overnight. The reaction solvent was evaporated, and the residue was coated onto Celite. The product was purified by column chromatography (2:1 DCM:heptane) to give a yellow solid (33% yield).

[0167] Synthesis of luminescent body 3

[0168] Synthesis of 2-(2'-chloro-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka] To a 2 L, three-necked round-bottom flask, 1-bromo-2-chlorobenzene and anhydrous tetrahydrofuran were added under nitrogen and cooled to -72 °C. n-BuLi was added, and the solution was warmed to RT. It was cooled again to -72 °C. n-BuLi was added, and the reaction was stirred for 1 h. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added, and the solution was warmed to RT and stirred overnight. The reaction was diluted with diethyl ether and aqueous HCl, the aqueous phase was extracted, and the combined organics were dried over MgSO4 and filtered. The residue was purified by column chromatography to give 2-(2'-chloro-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as a clear, yellow oil (80% yield).

[0169] Synthesis of 2''-chloro-2-fluoro-3-nitro-1,1':2',1''-terphenyl [ka] To a 2 L, three-necked round-bottom flask was added a solution of 2-(2'-chloro-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in dioxane / water, and the mixture was bubbled with nitrogen for 2 hours. Then, 1-bromo-2-fluoro-3-nitrobenzene, K2CO3, and Pd(PPh3)4 were added together. The reaction mixture was vigorously stirred at 95 °C. After 24 hours, the reaction was cooled to room temperature and diluted with EtOAc and brine. The aqueous phase was extracted with EtOAc. The combined organics were dried over MgSO4, filtered, and concentrated in vacuo to give a dark oil (63%).

[0170] Synthesis of 2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quaterphenyl]-2-amine: [ka] To a 2 L, three-necked round-bottom flask equipped with a septum and stir bar was added THF and KPO. 2″-Chloro-2-fluoro-3-nitro-1,1′:2′,1″-terphenyl, 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline, and SPhosPdG were then added together. The reaction mixture was vigorously stirred at 60 °C. After 24 h, the reaction mixture was cooled to RT, and EtOAc was added. The aqueous phase was extracted with EtOAc, and the combined organics were dried over MgSO, filtered, and concentrated in vacuo to give a viscous black oil, which was dissolved in dichloromethane and loaded onto a large silica gel plug to give 2′′-fluoro-3′′-nitro-[1,1′:2′,1'':2′′,1′′-quaterphenyl]-2-amine as a brown solid (83%).

[0171] Synthesis of 8-nitro-9H-tetrabenzo[b,d,f,h]azonine [ka] A solution of 2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quaterphenyl]-2-amine in DMSO was prepared in a 2 L round-bottom flask equipped with a septum and stir bar and stirred under nitrogen. K2CO3 was added and the reaction mixture was stirred vigorously at 150-160 °C. After 9 h, the reaction was cooled to RT and poured into DI water. The aqueous phase was extracted with EtOAc. The combined organics were washed with brine and dried over MgSO4. The reaction was filtered and concentrated in vacuo to afford 8-nitro-9H-tetrabenzo[b,d,f,h]azonine as an amber solid (85%).

[0172] Synthesis of 9H-tetrabenzo[b,d,f,h]azonine-8-amine [ka] A suspension of 8-nitro-9H-tetrabenzo[b,d,f,h]azonine in MeOH was prepared in a 2 L round-bottom flask equipped with a septum and stir bar. Pd / C and hydrazine hydrate were added under nitrogen, and the mixture was vigorously stirred at 60-65°C. After 3 h, it was cooled and filtered through a short pad of Celite. The filtrate was concentrated in vacuo to give a cream suspension. It was diluted with water, and the aqueous phase was extracted with dichloromethane. The combined organics were washed with water and brine and dried over MgSO4. The residue was filtered and concentrated in vacuo to give 9H-tetrabenzo[b,d,f,h]azonin-8-amine as a brown solid (84%).

[0173] Synthesis of 1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene [ka] 9H-Tetrabenzo[b,d,f,h]azonin-8-amine (1 g, 2.99 mmol) was dissolved in triethoxymethane (24.90 mL, 150 mmol) and sparged with argon for 5 minutes. Hydrogen chloride (0.295 mL, 3.59 mmol) (37% aqueous solution) was added in one portion at room temperature. The reaction was heated to 80° C. for 16 hours. The reaction was cooled to room temperature and concentrated under reduced pressure. The residue was diluted with ether and stirred for 30 minutes. The solid was collected by filtration to give the product (0.9 g, 89%) as a white solid.

[0174] Synthesis of 1-(4-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1-(tetrafluoro-15-boranyl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2-ide-1-ium-2-ide [ka] 1,2a-Diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene (0.85 g, 2.468 mmol) and 9-(4-(tert-butyl)pyridin-2-yl)-2-(4-(mesityl(tetrafluoro-15-boranyl)-13-indanyl)phenoxy)-9H-carbazole (2.324 g, 3.21 mmol) were combined in DMF (6 mL) in a pressure tube and sparged with nitrogen for 5 minutes. Bis(((trifluoromethyl)sulfonyl)oxy)copper (0.045 g, 0.123 mmol) was added to the mixture and sparged with nitrogen for 3 minutes. The tube was sealed and allowed to stir at 110° C. for 1 hour. The reaction was cooled to RT, diluted with DCM, and evaporated to dryness to give a brown oil. The material was purified by column chromatography to give the product (2.05 g, 95%).

[0175] Synthesis of luminescent body 3 [ka] 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1-(tetrafluoro-15-boranyl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2-ide-1-ium-2-ide (250 mg, 0.304 mmol), potassium tetrachloroplatinate (126 mg, 0.304 mmol), and 2,6-dimethylpyridine (130 mg, 1.215 mmol) were suspended in 1,2-dichlorobenzene (15 mL) in a round-bottom flask and sparged with nitrogen for 5 minutes. The flask was fitted with a condenser, and the reaction mixture was stirred under nitrogen at 125° C. for 24 hours. The reaction was cooled to RT and the product was purified by column chromatography (0.1 g, 36%).

[0176] Synthesis of luminescent material 4

[0177] 3-Bromo-[1,1'-biphenyl]-2-amine: [ka] To a suspension of 2,6-dibromoaniline (30 g, 117 mmol), phenylboronic acid (14.43 g, 117 mmol), sodium carbonate (74.6 g, 703 mmol), and Pd(PPh3)4 (6.84 g, 5.86 mmol) in toluene (1.2 L) in a 2 L round-bottom flask, ethanol (300 mL) and water (300 mL) were added. The flask was purged with nitrogen for 20 minutes, and the reaction mixture was stirred under reflux for 5 hours. The reaction was cooled to room temperature, and water (750 mL) was added, causing separation into two layers. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by column chromatography to give a white solid (86.31 g, 72%).

[0178] Synthesis of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-2-amine [ka]

[0179] A 2 L round-bottom flask was charged with 3-bromo-[1,1'-biphenyl]-2-amine (40 g, 156 mmol), potassium acetate (23.18 g, 234 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (84 g, 327 mmol), Pd(dppf)Cl.CHCl (6.41 g, 7.79 mmol), and dimethyl sulfoxide (1 L). The mixture was purged with nitrogen for 20 minutes and then heated to 80 °C for 3.5 hours. The reaction was cooled to room temperature, and saturated aqueous ammonium chloride and ethyl acetate were added to the reaction mixture. The two layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with 1 L of NaCl solution, dried over MgSO4, filtered, concentrated in vacuo and the oil was purified by column chromatography to give the product as a pale yellow solid (37.7 g, 77%).

[0180] Synthesis of 2-fluoro-3-nitro-[1,1':2',1'':2'',1''':3''',1''''-quinquephenyl]-2''''-amine [ka] To a 2 L round-bottom flask were added tetrahydrofuran (380 ml), tripotassium phosphate (573 ml, 287 mmol) (0.5 M aqueous solution), 2″-chloro-2-fluoro-3-nitro-1,1′:2′,1″-terphenyl (40 g, 110 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1′-biphenyl]-2-amine (44.9 g, 144 mmol), and Sphos-Pd-G2 (4.12 g, 5.60 mmol), and the reaction mixture was stirred at 60° C. under nitrogen overnight. The reaction mixture was cooled to RT. Ethyl acetate was added, and the two layers were separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and concentrated. The residue was purified by column chromatography to give the product as a yellow solid. The solid was suspended in heptane and stirred for 3 hours. The suspension was filtered and washed with heptane to give the product as a yellow solid (47.85 g, 92%).

[0181] Synthesis of 8-nitro-10-phenyl-9H-tetrabenzo[b,d,f,h]azonine [ka] To a 2 L round-bottom flask containing a solution of 2-fluoro-3-nitro-[1,1':2',1'':2'',1''':3'',1''''-quinquphenyl]-2''''-amine (32 g, 66.0 mmol) in dimethyl sulfoxide (1000 ml) was added potassium carbonate (18.25 g, 132 mmol), and the flask was purged with nitrogen for 30 minutes. The reaction mixture was then stirred at 155 °C overnight. The reaction was cooled to RT, and cold saturated aqueous sodium chloride and ethyl acetate were added. The aqueous layer was extracted several times with ethyl acetate. The organic layers were combined and degassed to give an oil that was purified by column chromatography. The solid was suspended in heptane and stirred for 2 days. The suspension was filtered, and the solid was washed twice with heptane to give the product as an orange-yellow solid (37.15 g, 64%).

[0182] Synthesis of 10-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] To a 2 L round-bottom flask containing a suspension of 8-nitro-10-phenyl-9H-tetrabenzo[b,d,f,h]azonine (36.5 g, 81 mmol) in methanol (1.25 L) under N2, Pd / C (8.62 g, 8.10 mmol, 10% wt) was added, followed by hydrazine hydrate (101 mL, 1619 mmol), and the mixture was vigorously stirred under nitrogen at 70 °C (oil bath) for 5 h. The reaction was cooled to RT, and the mixture was filtered through a short pad of Celite, washing with methanol (100 mL) followed by dichloromethane (4 × 250 mL). The product was purified by column chromatography to give an off-white solid (31.55 g, 94%).

[0183] Synthesis of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] Sodium tert-butoxide (0.489 g, 5.09 mmol), 10-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine (0.697 g, 1.697 mmol), and 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (0.8 g, 1.697 mmol) were charged to a 250 mL round-bottom flask and flushed with N. Toluene (6.79 ml) and Sphos-Pd-G (0.066 g, 0.085 mmol) were then added and the reaction was stirred at reflux. The reaction was cooled to RT, filtered, and degassed. The product was purified by column chromatography (1.3 g, 88% yield).

[0184] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium bromide: [ka] N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine (45.9 g, 57.3 mmol) was dissolved in refluxing triethoxymethane (95 ml, 573 mmol) and cooled to RT. Hydrogen bromide (7.08 ml, 63.0 mmol) was added and the mixture was stirred at RT overnight. The solvent was removed in vacuo and the material purified by column chromatography to give the product as an off-white solid (34.22 g, 63.6% yield).

[0185] Synthesis of luminescent material 4 [ka] In a 250 mL round-bottom flask, 1,3,5-trimethoxybenzene (0.489 g, 2.90 mmol), 2,6-dimethylpyridine (2.243 mL, 19.36 mmol), 2-bromo-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3-phenyl-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene (15.7 g, 17.60 mmol), and Pt(acac) (6.92 g, 17.60 mmol) were dissolved / suspended in propionic acid (37 mL, 17.60 mmol). The reaction was heated at 150 °C overnight. The reaction was filtered and the filtered solid was redissolved in DCM and partitioned with water. The organic layer was retained, concentrated and isolated by column chromatography to give a yellow solid (12.1 g, 67.6% yield).

[0186] Synthesis of luminescent body 5

[0187] Synthesis of 4-bromo-2-(tert-butyl)aniline: [ka] In a 1 L round-bottom flask, 2-(tert-butyl)aniline (50 g, 328 mmol) was solubilized in acetonitrile (1.3 L) and the flask was purged with nitrogen for 20 minutes. Ammonium acetate (2.61 g, 32.8 mmol) was then added, followed by NBS (62.0 g, 345 mmol) in ten 6.2 g portions every 10 minutes. A saturated aqueous solution of NaSO (1.5 L) was added along with ethyl acetate, and the layers were separated. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over MgSO, filtered, and concentrated in vacuo. The residue was purified by column chromatography to give the product as a red oil (72.5 g, 97%).

[0188] Synthesis of 4-bromo-2-(tert-butyl)-6-chloroaniline [ka] A 2 L round-bottom flask was charged with 4-bromo-2-(tert-butyl)aniline (63 g, 276 mmol) and DMF (1.05 L). The reaction mixture was purged with nitrogen for 20 minutes. NCS (41.4 g, 304 mmol) was then added in one portion, and the flask was purged with nitrogen for 5 minutes. The reaction mixture was then stirred at 73 °C under nitrogen for 4 hours. A saturated aqueous solution of NaSO was added along with ethyl acetate, and the layers were separated. The organic layer was washed with water, dried over MgSO, filtered, and concentrated in vacuo to give the product as a red oil (69.4 g, 94%).

[0189] Synthesis of 2-(tert-butyl)-6-chloroaniline [ka] A 350 mL pressure vessel was charged with 4-bromo-2-(tert-butyl)-6-chloroaniline (20 g, 76 mmol), palladium on carbon (8.11 g, 7.62 mmol), and ethanol (160 mL). The reaction mixture was placed under 10 psi of H for 4 hours. The mixture was filtered through a pad of Celite and washed with ethanol. The filtrate was concentrated in vacuo. A saturated aqueous solution of sodium bicarbonate and ethyl acetate were added, and the layers were separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO, filtered, and concentrated in vacuo to give the product as an orange-yellow oil (14.05 g, 81%).

[0190] Synthesis of 2-(tert-butyl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline [ka] To a 2 L round-bottom flask were added 2-(tert-butyl)-6-chloroaniline (25 g, 136 mmol) and 1,4-dioxane (550 mL), followed by Pd2dba3 (3.21 g, 3.40 mmol), dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphane (6.62 g, 13.61 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (105 g, 408 mmol), and potassium acetate (40.5 g, 408 mmol). The flask was purged with nitrogen for 20 minutes, and the reaction mixture was then refluxed under nitrogen for 4 hours. After 4 hours, the mixture was filtered through a thin pad of Celite, washing with ethyl acetate, and the filtrate was concentrated in vacuo. The product was purified by column chromatography to give an orange-yellow oil (26.2 g, 63%).

[0191] Synthesis of 3-(tert-butyl)-2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quaterphenyl]-2-amine [ka] A 500 mL round-bottom flask was charged with tetrahydrofuran (63 mL), freshly prepared aqueous potassium phosphate tribasic solution (96 mL, 47.8 mmol) (0.5 M aqueous solution), 2″-chloro-2-fluoro-3-nitro-1,1′:2′,1″-terphenyl (6 g, 18.31 mmol), 2-(tert-butyl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (13.99 g, 45.8 mmol), and Sphos Pd G2 (0.673 g, 0.934 mmol), and the flask was purged with nitrogen for 30 minutes. The reaction mixture was then vigorously stirred at 60° C. under nitrogen for 20 hours. The reaction was then cooled to room temperature, ethyl acetate was added, and the layers were separated, after which the aqueous layer was further extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The product was purified by column chromatography to give the product as a yellow solid (9.63 g, 78%).

[0192] Synthesis of 8-(tert-butyl)-10-nitro-9H-tetrabenzo[b,d,f,h]azonine [ka] To a 1 L round-bottom flask containing a solution of 3-(tert-butyl)-2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quaterphenyl]-2-amine (11 g, 23.75 mmol) in anhydrous dimethyl sulfoxide (385 ml) was added cesium carbonate (23.45 g, 71.2 mmol), and the flask was purged with nitrogen for 20 minutes. The reaction mixture was then vigorously stirred at 150 °C for 5 hours. The reaction was cooled to RT. Ice-cold saturated aqueous sodium chloride solution was added, followed by ethyl acetate. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and then concentrated in vacuo to give an oil, which was purified by column chromatography to give the product as an orange-yellow solid (4.79 g, 48%).

[0193] Synthesis of 10-(tert-butyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] To a 1 L round-bottom flask equipped with a condenser and septum containing a solution of 8-(tert-butyl)-10-nitro-9H-tetrabenzo[b,d,f,h]azonine (8.8 g, 20.93 mmol) in methanol (325 mL) under nitrogen, palladium on carbon (2.227 g, 2.093 mmol, 10 wt%) was added, followed by hydrazine hydrate (26.1 mL, 419 mmol), and the mixture was vigorously stirred at 65°C under nitrogen overnight. The mixture was filtered through a short pad of Celite and washed with methanol and dichloromethane. A pale orange-yellow solid was obtained, which was purified by column chromatography to give the product as an off-white solid (7.29 g, 89%).

[0194] Synthesis of 10-(tert-butyl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] A mixture of 10-(tert-butyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine (2.0 g, 5.12 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (2.66 g, 5.63 mmol), and BINAP Pd Gen3 (0.254 g, 0.256 mmol) in anhydrous toluene was sparged with nitrogen for 30 minutes. After adding sodium 2-methylpropan-2-olate (0.984 g, 10.24 mmol), the reaction was refluxed for 20 hours. The reaction was quenched with saturated ammonium chloride and diluted with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by column chromatography to give 10-(tert-butyl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine (3 g, 75%) as an off-white solid.

[0195] Synthesis of 3-(tert-butyl)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium chloride [ka]

[0196] Hydrochloric acid (0.533 ml, 6.15 mmol) was added to a solution of 10-(tert-butyl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine (3 g, 3.84 mmol) in triethyl orthoformate (32.0 ml, 192 mmol). The reaction was heated at 100° C. for 2 hours. The volatiles were removed under reduced pressure and the residue was triturated with hexane to give the product as an off-white solid (2.7 g, 85%).

[0197] Synthesis of luminescent body 5 JPEG0007799418000151.jpg39115 A mixture of potassium tetrachloroplatinate(II) (1.104 g, 2.66 mmol), ligand (2.0 g, 2.417 mmol), and 2,6-lutidine (0.929 mL, 7.98 mmol) in glacial acetic acid (48.3 mL) was sparged with nitrogen for 40 minutes. The reaction was then refluxed overnight. The reaction mixture was diluted with a mixture of methanol / water. The precipitate was collected by filtration, washed on the filter, and dried. The product was purified by column chromatography (1.1 g) to give a yellow solid.

[0198] Synthesis of luminescent material 6 Synthesis of N-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] Sodium tert-butoxide (3.27 g, 34.0 mmol), 9H-tetrabenzo[b,d,f,h]azonin-8-amine (3.77 g, 11.27 mmol), and 2-(3-chlorophenoxy)-9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazole (6.5 g, 11.34 mmol) were added to a 250 mL round-bottom flask and flushed with nitrogen. Toluene (90 ml) was added and the reaction heated to 80 °C. SphosPdG3 (0.442 g, 0.567 mmol) was then added and the reaction brought to reflux. After 2 h, the reaction was cooled, filtered through Celite, and purified by column chromatography to give a purple solid (8 g, 79%).

[0199] Synthesis of 1-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium [ka] N-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine (8 g, 9.18 mmol) was dissolved in triethoxymethane (24 mL, 144 mmol), refluxed, and cooled to RT. Hydrogen bromide (1.341 mL, 11.94 mmol) was then added, giving a suspension after 2 h. The suspension was heated to 65° C. and MTBE (50 mL) was added. The suspension was cooled, and the product was purified by column chromatography to give an off-white solid (2.5 g, 28.3%).

[0200] Synthesis of luminescent material 6 [ka] A mixture of Pt(acac) (2.1 g, 5.34 mmol), 2,6-dimethylpyridine (0.292 mL, 2.52 mmol), and 2-bromo-1-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene (2.02 g, 2.1 mmol) in AcOH (20 mL) was sparged with nitrogen, and the reaction was heated to reflux overnight. The reaction was cooled to RT, and water was added to give a precipitate. The precipitate was purified by column chromatography to give a yellow solid (0.96 g, 46%).

[0201] Synthesis of luminescent material 7 Synthesis of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] A mixture of 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole (2.59 g, 5.12 mmol), 10-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine (2.0 g, 4.87 mmol), and sodium 2-methylpropan-2-olate (0.936 g, 9.74 mmol) was sparged with nitrogen before adding BINAP-PdG (0.242 g, 0.244 mmol). The reaction was heated at 95 °C overnight. The reaction mixture was quenched with saturated ammonium chloride. The resulting slurry was filtered through a plug of Celite and washed with dichloromethane. The filtrate was partitioned between water and DCM, and the aqueous layer was extracted three times with DCM. The combined organic layers were dried over sodium sulfate and purified by column chromatography to give an off-white solid (2.43 g, 59%).

[0202] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-3-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium chloride [ka] Hydrochloric acid (0.388 ml, 4.65 mmol) was added to a mixture of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine (2.43 g, 2.91 mmol) in triethyl orthoformate (24.22 ml, 145 mmol). The reaction mixture was heated at 100° C. for 1 hour. The solvent was removed under reduced pressure and the residue was triturated with heptane and dried in vacuo to give an off-white solid (1.8 g, 70.2%). [ka] A mixture of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-3-phenyl-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-1-ium chloride (1.8 g, 2.041 mmol), potassium tetrachloroplatinate(II) (0.932 g, 2.245 mmol), and 2,6-lutidine (0.785 mL, 6.74 mmol) in acetic acid (40.8 mL) was sparged with nitrogen. The reaction was then refluxed overnight. The reaction mixture was cooled to RT, and water was added to give a precipitate. The precipitate was collected by filtration, the filter cake was washed with water, and dried by suction filtration. The solid was purified by column chromatography to give a yellow solid (1.2 g, 56.6%).

[0203] Synthesis of luminescent material 7 [ka] A solution of potassium phosphate hydrate (0.532 g, 2.311 mmol) in 1,4-dioxane (7.43 mL) / water (0.825 mL) was sparged with nitrogen. Platinum complex (0.6 g, 0.578 mmol), SPhos-PdG2 (0.048 g, 0.058 mmol), and (phenyl-d5)boronic acid (0.293 g, 2.311 mmol) were added. The resulting slurry was sparged with nitrogen, and the reaction was heated at 100 °C overnight. The reaction was cooled to RT, and the solvent was removed in vacuo. The product was purified by column chromatography to give a yellow solid (0.44 g, 70.2%).

[0204] Synthesis of luminescent body 8 [ka] To a 20 mL vial equipped with a stir bar was added a solution of (4-(tert-butyl)phenyl)boronic acid (0.411 g, 2.311 mmol), SPhos-PdG2 (0.042 g, 0.058 mmol), and potassium phosphate monohydrate (0.532 g, 2.311 mmol) in 1,4-dioxane (5.59 mL) / water (0.621 mL) (10:1). The mixture was sparged with nitrogen and then heated to 100 °C overnight. The reaction was cooled to RT and filtered through Celite. The filtrate was concentrated under reduced pressure and purified by column chromatography to give a yellow solid (0.58 g, 88%).

[0205] Synthesis of luminescent body 9 [ka] To a 20 mL vial equipped with a stir bar was added a solution of (3,5-di-tert-butylphenyl)boronic acid (0.541 g, 2.311 mmol), SPhos-PdG2 (0.042 g, 0.058 mmol), and potassium phosphate monohydrate (0.532 g, 2.311 mmol) in 1,4-dioxane (5.59 mL) / water (0.621 mL) (10:1). The reaction was sparged with nitrogen and heated to 100 °C overnight. The reaction was cooled to RT and filtered through Celite. The filtrate was concentrated under reduced pressure and purified by column chromatography to give a yellow solid (0.61 g, 87%).

[0206] Synthesis of luminescent body 10 Synthesis of 2'-bromo-2-fluoro-3-nitro-1,1'-biphenyl [ka] A 1-L round-bottom flask was charged with (2-bromophenyl)boronic acid (21.90 g, 106 mmol), 1-bromo-2-fluoro-3-nitrobenzene (25 g, 111 mmol), sodium carbonate (47.2 g, 445 mmol), Pd(PPh3)4 (6.43 g, 5.57 mmol), toluene (255 mL), ethanol (85 mL), and water (170 mL). The reaction mixture was purged with nitrogen for 30 minutes with vigorous stirring, and then the reaction mixture was stirred at 85 °C overnight. The reaction was cooled to RT. After water was added, the two layers were separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The product was purified by column chromatography to give a white solid (86 g, 91%).

[0207] Synthesis of 2-chloro-2''-fluoro-3-methoxy-3''-nitro-1,1':2',1''-terphenyl [ka] A 2 L round-bottom flask was charged with 2'-bromo-2-fluoro-3-nitro-1,1'-biphenyl (40.4 g, 137 mmol), (2-chloro-3-methoxyphenyl)boronic acid (25 g, 130 mmol), SPhosPdG2 (2.81 g, 3.90 mmol), tetrahydrofuran (600 mL), and potassium phosphate (800 mL, 400 mmol, 0.5 M aqueous solution). The reaction mixture was purged with nitrogen for 30 minutes and then stirred at 60 °C for 5 hours under nitrogen. The reaction was cooled to RT. Water (1 L) was added, and the two layers separated. The aqueous layer was extracted with ethyl acetate (3 × 300 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The crude material was purified by column chromatography to give a white solid (80.3 g, 95%).

[0208] Synthesis of 2'''-fluoro-6'-methoxy-3'''-nitro-[1,1':2',1'':2'',1'''-quaterphenyl]-2-amine [ka] To a 2 L round-bottom flask was added 2-chloro-2"-fluoro-3-methoxy-3"-nitro-1,1':2',1"-terphenyl (40 g, 112 mmol), dioxane (450 mL), and 0.5 M potassium phosphate (700 mL, 350 mmol). The reaction mixture was purged with nitrogen for 30 minutes. Then, 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (62.5 g, 280 mmol) and SPhosPdG2 (4.11 g, 5.59 mmol) were added, and the reaction mixture was stirred at 90 °C for 16 hours. The reaction was cooled to RT. After the addition of water (2 L) and ethyl acetate (500 mL), the two layers were separated. The aqueous layer was extracted with ethyl acetate (3 x 500 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The crude material was purified by column chromatography to give an off-white solid (61.3 g, 67%).

[0209] Synthesis of 4-methoxy-10-nitro-9H-tetrabenzo[b,d,f,h]azonine [ka] To a 2 L round-bottom flask containing a solution of 2'''-fluoro-6'-methoxy-3'''-nitro-[1,1':2',1'':2'',1'''-quaterphenyl]-2-amine (28 g, 61.8 mmol) in dry DMSO (1 L) was added cesium carbonate (61.0 g, 185 mmol), and the flask was purged with nitrogen. The reaction mixture was then stirred at 160 °C for 3 h. The reaction was cooled to room temperature. 4 L of ice-cold saturated NaCl solution was added, followed by 750 mL of ethyl acetate, and the two layers separated. The aqueous layer was extracted with ethyl acetate (4 × 500 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo at 45 °C to give a maroon viscous oil. The crude material was purified by column chromatography to give an orange-yellow solid (51.4 g, 85%).

[0210] Synthesis of 10-nitro-9H-tetrabenzo[b,d,f,h]azonin-4-ol [ka] To a heated (165°C) solution of pyridine hydrochloride (200 g, 1731 mmol) in a 1 L round-bottom flask was added 4-methoxy-10-nitro-9H-tetrabenzo[b,d,f,h]azonine (20 g, 50.7 mmol) with stirring. The reaction mixture was stirred at 170°C for 4 hours. After 4 hours, the hot solution was poured directly into water (1 L). The resulting suspension was filtered and washed with water (2 x 200 mL) to give a brown solid. The crude material was purified by column chromatography to give a red solid (35.7 g, 68%).

[0211] Synthesis of 10-nitro-9H-tetrabenzo[b,d,f,h]azonin-4-yl trifluoromethanesulfonate [ka] A 2 L round-bottom flask was charged with 10-nitro-9H-tetrabenzo[b,d,f,h]azonin-4-ol (25 g, 63.7 mmol) and dry dichloromethane (600 mL). After purging the flask with nitrogen, triethylamine (17.77 mL, 127 mmol) was added. The reaction mixture was stirred at RT for 15 minutes and then cooled to 0 °C using an ice-water bath. Trifluoromethanesulfonic anhydride (11.26 mL, 66.9 mmol) was then added dropwise over 50 minutes. The reaction mixture was slowly warmed to RT and stirred at room temperature for 16 hours. A saturated aqueous solution of sodium bicarbonate (1 L) was added, and the two layers separated. The aqueous layer was extracted with dichloromethane (3 × 300 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The crude material was purified by column chromatography to yield an orange solid (50.7 g, 97%).

[0212] Synthesis of 10-nitro-4-phenyl-9H-tetrabenzo[b,d,f,h]azonine [ka] A 1 L round-bottom flask was charged with 10-nitro-9H-tetrabenzo[b,d,f,h]azonin-4-yl trifluoromethanesulfonate (15 g, 29.3 mmol), phenylboronic acid (7.14 g, 58.5 mmol), SPhosPdG2 (0.633 g, 0.878 mmol), tetrahydrofuran (135 mL), and potassium phosphate (180 mL, 90 mmol, 0.5 M aqueous solution). The flask was purged with nitrogen for 20 minutes, and the reaction mixture was stirred under nitrogen at 60 °C for 3 hours. After 3 hours, the reaction mixture was cooled to room temperature. After the addition of water (500 mL), the two layers separated. The aqueous layer was extracted with ethyl acetate (3 × 250 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The crude material was purified by column chromatography to yield a red solid (16.8 g, 96%).

[0213] Synthesis of 14-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] To a 2 L round-bottom flask containing a suspension of 8-nitro-4-phenyl-9H-tetrabenzo[b,d,f,h]azonine (16.8 g, 38.1 mmol) in methanol (650 mL) under nitrogen, Pd / C (4.06 g, 3.81 mmol) was added, followed by hydrazine hydrate (47.5 mL, 763 mmol), and the mixture was stirred at 66 °C under nitrogen for 2 h. After 2 h, the reaction was cooled to RT. The mixture was filtered through a short pad of Celite, washing with methanol (100 mL) followed by dichloromethane (4 × 200 mL). The filtrate was concentrated in vacuo, and the resulting solid was purified by column chromatography to give an off-white solid (15.42 g, 97%).

[0214] Synthesis of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-14-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] A mixture of 10-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine (1.5 g, 2.60 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.756 g, 3.39 mmol), and BINAPPdG3 (0.153 g, 0.154 mmol) in anhydrous toluene was sparged with nitrogen for 30 minutes. Sodium 2-methylpropan-2-olate (0.592 g, 6.17 mmol) was then added, and the reaction was refluxed for 20 hours. The crude reaction was filtered through Celite, rinsed with DCM (25 mL), and concentrated under reduced pressure to give a yellow-green solid (3.4 g, 87%).

[0215] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-7-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium [ka] Hydrochloric acid (0.531 ml, 6.37 mmol) was added to a mixture of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-13-phenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine (3.4 g, 4.24 mmol) in triethyl orthoformate (21.20 ml, 127 mmol). The reaction mixture was heated at 100° C. for 1 hour. The solvent was removed under reduced pressure and the residue was triturated with heptane and dried in vacuo to give an off-white solid (3.0 g, 83%).

[0216] Synthesis of luminescent body 10 [ka] A mixture of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-6-phenyl-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-1-ium chloride (2.5 g, 2.95 mmol), potassium tetrachloroplatinate(II) (1.347 g, 3.24 mmol), and 2,6-dimethylpyridine (1.134 mL, 9.73 mmol) in acetic acid (59.0 mL) was sparged with nitrogen for 40 minutes. The reaction was then refluxed overnight. The reaction was cooled to RT, and a mixture of water and methanol was added. The precipitate was collected by filtration and purified by column chromatography to give a yellow solid (2.6 g, 87%).

[0217] Synthesis of luminescent material 11 Synthesis of 2-fluoro-3''-methoxy-3-nitro-[1,1':2',1'':2'',1''':3'''',1''''-quinquephenyl]-2''''-amine: [ka] To a suspension of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-2-amine (23.60 g, 80 mmol), 2-chloro-2"-fluoro-3-methoxy-3"-nitro-1,1':2',1"-terphenyl (14.3 g, 40.0 mmol), and SphosPdG2 (1.440 g, 1.999 mmol) in dioxane (240 mL) was added potassium phosphate (480 mL, 240 mmol) under nitrogen. The reaction mixture was heated to 90 °C for 3 h. After cooling, the reaction mixture was quenched with water (50 mL) and extracted with ethyl acetate (50 mL). The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (50 mL). The combined organic layers were concentrated in vacuo and the residue was purified by column chromatography to give the desired product (13.4 g, 68%).

[0218] Synthesis of 4-methoxy-10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonine [ka] A mixture of 2-fluoro-3''-methoxy-3-nitro-[1,1':2',1'':2'',1''':3'',1''''-quinquephenyl]-2''''-amine (13.4 g, 27.3 mmol) and cesium carbonate (26.7 g, 82 mmol) in DMSO (500 mL) was heated to 150 °C for 3 h. After cooling, the reaction was quenched with water (300 mL) and then extracted with ethyl acetate (300 mL). The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (300 mL). The combined organic layers were concentrated, and the residue was purified by column chromatography to give the desired product as an orange solid (8.76 g, 68%).

[0219] Synthesis of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonin-4-ol [ka] A mixture of pyridine hydrochloride (246 g, 2125 mmol) and 4-methoxy-10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonine (10 g, 21.25 mmol) was heated to 165° C. for 3 h. After cooling, water (200 mL) and ethyl acetate (200 mL) were added with stirring. The organic layer was collected and the solvent was removed. The residue was purified by column chromatography to give an orange powder (6.5 g, 67%).

[0220] Synthesis of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonin-4-yl trifluoromethanesulfonate [ka] To a suspension of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonin-4-ol (7 g, 15.33 mmol) and triethylamine (4.66 g, 46.0 mmol) in CHCl (200 mL) was added trifluoromethanesulfonic anhydride (8.65 g, 30.7 mmol) at 0 °C. The reaction mixture was then diluted with CHCl (100 mL) and washed with water (100 mL × 2). The solvent was then removed, and the residue was purified by column chromatography to give an orange solid (8.1 g, 90%).

[0221] Synthesis of 10-nitro-4,8-diphenyl-9H-tetrabenzo[b,d,f,h]azonine [ka] To a solution of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonin-4-yl trifluoromethanesulfonate (3.6 g, 6.12 mmol), phenylboronic acid (1.492 g, 12.23 mmol), and SphosPdG2 (0.220 g, 0.306 mmol) in dioxane (60 mL) was added aqueous potassium phosphate (122 mL, 61.2 mmol) under nitrogen. The reaction mixture was heated to 80 °C for 3 h. After cooling, ethyl acetate (100 mL) and water (50 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with methylene chloride (100 mL). The combined organic layers were concentrated, and the residue was purified by column chromatography to give the desired compound (2 g, 60%).

[0222] Synthesis of 10,14-diphenyl-9H-tetrabenzo[b,d,f,h]azonine-8-amine [ka] A mixture of 10-nitro-4,8-diphenyl-9H-tetrabenzo[b,d,f,h]azonine (2 g, 3.87 mmol), hydrazine hydrate (3.88 g, 77 mmol), and palladium (0.412 g, 0.387 mmol) on carbon in EtOH (200 mL) / CHCl (20 mL) was heated to 90 °C for 3 h. After cooling, the reaction mixture was filtered through Celite and washed with ethyl acetate. All solvents were removed, and the residue was purified by column chromatography to give the desired product (1.2 g, 63%).

[0223] Synthesis of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-10,14-diphenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] A mixture of 10,14-diphenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine (1.5 g, 3.08 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.756 g, 3.39 mmol), and BINAP Pd Gen3 (0.153 g, 0.154 mmol) in anhydrous toluene was sparged with nitrogen for 30 minutes. Sodium 2-methylpropan-2-olate (0.592 g, 6.17 mmol) was added and sparging continued for 10 minutes. The reaction was then refluxed for 20 hours. The crude reaction was filtered through Celite, rinsed with DCM (25 mL), and concentrated under reduced pressure to give a yellow-green solid (1.8 g, 58%).

[0224] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3,7-diphenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium [ka] HCl (0.222 ml, 7.30 mmol) was added to a solution of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-10,14-diphenyl-9H-tetrabenzo[b,d,f,h]azonin-8-amine (4 g, 4.56 mmol) in triethyl orthoformate (38.0 ml, 228 mmol). The reaction was heated at 100° C. for 3 hours to achieve complete conversion. Volatiles were removed under reduced pressure to give a white solid (5.1 g, 4.25 mmol, 93%).

[0225] Synthesis of luminescent material 11 [ka] A mixture of potassium tetrachloroplatinate (2.52 g, 6.07 mmol), 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3,7-diphenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium chloride (5.1 g, 5.52 mmol), and 2,6-dimethylpyridine (2.100 mL, 18.22 mmol) in AcOH (110 mL) was sparged with nitrogen for 40 minutes. The reaction was then refluxed at 120° C. for 18 hours. The combined mixture was diluted with water (150 mL) and extracted with DCM (3×150 mL). The crude material was concentrated and the product was purified by column chromatography to give a yellow solid (1.2 g, 18.11%).

[0226] Synthesis of luminescent material 12 Synthesis of 2-chloro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline [ka] A suspension of 2-bromo-6-chloroaniline (8.2 g, 39.7 mmol), bis(pinacolato)diboron (30.3 g, 119 mmol), and KOAc (15.59 g, 159 mmol) in DMSO (80 mL) was added under nitrogen to Pd(dppf)Cl * CHCl (1.622 g, 2 mmol) was added. The reaction mixture was then heated to 90° C. under nitrogen for 20 h. After cooling, ethyl acetate (200 mL) and aqueous HCl (0.5 M, 100 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic layers were washed with brine (100 mL × 2). The organic solution was then dried over NaSO. After removal of the solvent, the residue was purified by column chromatography to give a white solid (8.1 g, 80%).

[0227] Synthesis of 2-(2'-bromo-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka] To a solution of 2,2'-dibromo-1,1'-biphenyl (15 g, 48.1 mmol) in anhydrous THF (500 mL) was added n-BuLi (23 mL, 2.5 M, 27.5 mmol) dropwise at -78 °C under nitrogen. After the addition, the reaction mixture was stirred for 1 hour, and then a solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.63 g, 62.5 mmol) in anhydrous THF (10 mL) was added slowly at -78 °C. After the addition, the reaction temperature was gradually returned to room temperature and stirred for an additional 2 hours. Water (200 mL) and ethyl acetate (200 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (200 mL). The solvent from the combined organic layers was removed, and the residue was purified by column chromatography to give the desired product (11 g, 64%).

[0228] Synthesis of 2''-bromo-2-fluoro-3-nitro-1,1':2',1''-terphenyl [ka] To a suspension of 1-bromo-2-fluoro-3-nitrobenzene (10.04 g, 45.6 mmol), boronate 268-4 (12.6 g, 35.1 mmol), and aqueous KCO (70.2 mL, 2 M, 140.4 mmol) in dioxane (140 mL) was added Pd(PhP) (2.028 g, 1.755 mmol) under N. The reaction mixture was heated to 85 °C overnight under nitrogen. After cooling, ethyl acetate (150 mL) and water (150 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (150 mL). The solvent from the combined organic layers was removed, and the residue was purified by column chromatography (9 g, 68%).

[0229] 3-chloro-2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quaterphenyl]-2-amine [ka] To a solution of 2-chloro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (2.4 g, 9.46 mmol), 2″-bromo-2-fluoro-3-nitro-1,1′:2′,1″-terphenyl (3.2 g, 8.6 mmol), and SphosPdG2 (0.31 g, 0.43 mmol) in THF (55 mL) was added an aqueous solution of K3PO4 (103 mL, 0.5 M, 51.6 mmol) under N2. The reaction mixture was heated to 60 °C for 3 h. After cooling, ethyl acetate (50 mL) and water (50 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (50 mL). The solvent of the combined organic layers was removed. The residue was purified by column chromatography to give the desired product (2.8 g, 78%).

[0230] Synthesis of 8-chloro-10-nitro-9H-tetrabenzo[b,d,f,h]azonine [ka] Cs2CO3 (17.5 g, 53.7 mmol) was added to a DMSO solution of 3-chloro-2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quaterphenyl]-2-amine (7.5 g, 17.9 mmol). The reaction mixture was heated to 150 °C (oil bath temperature) for 3 h. After cooling, the reaction was quenched with water (100 mL) and then extracted with ethyl acetate (100 mL × 2). The combined organic solution was washed with brine (100 mL × 2). The solvent was then removed in vacuo, and the residue was purified by column chromatography to give an orange solid product (5.2 g, 72.8%).

[0231] Synthesis of 8-([1,1':3',1''-terphenyl]-5'-yl)-10-nitro-9H-tetrabenzo[b,d,f,h]azonine [ka] Under N2, an aqueous solution of K3PO4 (211 mL, 0.5 M, 105 mmol) was added to a suspension of 8-chloro-10-nitro-9H-tetrabenzo[b,d,f,h]azonine (6 g, 15.04 mmol), terphenylboronic acid 268-8 (8.25 g, 30.1 mmol), and SphosPdG2 (1.084 g, 1.5 mmol) in dioxane (100 mL). The reaction mixture was heated to 90 °C for 3 h. After cooling, ethyl acetate (100 mL) and water (50 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (100 mL). The solvent from the combined organic layers was removed, and the residue was purified by column chromatography to give a solid product (8.92 g, 100%).

[0232] Synthesis of 10-([1,1':3',1''-terphenyl]-5'-yl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine [ka] Pd / C (1 g, 10%, 0.945 mmol) was added to a solution of 8-([1,1':3',1''-terphenyl]-5'-yl)-10-nitro-9H-tetrabenzo[b,d,f,h]azonine (2.8 g, 4.72 mmol) and hydrazine hydrate (11.82 g, 236 mmol) in a mixed solvent system of ethanol (100 mL) and CHCl (20 mL). The reaction mixture was heated to reflux for 3 h. After cooling, the reaction mixture was filtered through Celite and washed with CHCl (20 mL × 5). The solvent was removed, and the residue was purified by column chromatography to give the product as an off-white solid (1.35 g, 50%).

[0233] Synthesis of 10-([1,1':3',1''-terphenyl]-5'-yl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine: [ka] A mixture of 10-([1,1':3',1''-terphenyl]-5'-yl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine (1.5 g, 2.67 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.519 g, 2.93 mmol), and BINAPPdG3 (0.132 g, 0.133 mmol) in anhydrous toluene was sparged with nitrogen for 30 minutes. Sodium 2-methylpropan-2-olate (0.512 g, 5.33 mmol) was then added and sparging continued for 10 minutes. The reaction was then refluxed for 20 hours. The reaction was quenched with saturated ammonium chloride (20 mL) and diluted with ethyl acetate (20 mL). The resulting slurry was filtered through a plug of Celite (0.5''). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (2 x 20 mL). The combined organic layers were washed with saturated brine (50 mL), dried over anhydrous sodium sulfate (12 g), and concentrated. The residue was purified by column chromatography to give an off-white solid (2.32 g, 89%).

[0234] Synthesis of 3-([1,1':3',1''-terphenyl]-5'-yl)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium [ka] HCl (0.118 ml, 3.89 mmol) was added to a solution of 10-([1,1':3',1''-terphenyl]-5'-yl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonin-8-amine (2.32 g, 2.434 mmol) in triethyl orthoformate (20.26 ml, 122 mmol). The reaction was heated to 100°C for 16 hours. Volatiles were removed under reduced pressure and the residue was triturated with warm hexanes (2 x 25 mL) to give an off-white solid (2.35 g, 85% yield).

[0235] Synthesis of luminescent material 12 [ka] A mixture of potassium tetrachloroplatinate (0.228 g, 0.550 mmol), 3-([1,1':3',1''-terphenyl]-5'-yl)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]inden-2a-ium chloride (0.5 g, 0.500 mmol), and 2,6-dimethylpyridine (0.190 mL, 1.651 mmol) in AcOH (10.00 mL) was sparged with nitrogen for 40 minutes. The reaction was refluxed at 120 °C overnight. The reaction mixture was diluted with water, and the aqueous layer was extracted several times with DCM. The combined organic layers were dried and concentrated, and the residue was purified by column chromatography to give a yellow solid (1.6 g, 73%).

[0236] Device Data

[0237] Eight OLED devices were fabricated to compare the performance of several exemplary compounds of the present invention with comparative compounds in OLED applications. OLED1 through OLED7 contained exemplary compounds of the present invention, Emitter 2, Emitter 3, Emitter 6, Emitter 4, Emitter 5, and Emitter 7, respectively, as emitter compounds, and OLED8 contained the comparative compound as the emitter compound. Device performance data are shown in Table 1 below.

[0238] OLEDs were grown on glass substrates precoated with an indium-tin-oxide (ITO) layer with a sheet resistance of 15 Ω / sq. Prior to deposition or coating of the organic layers, the substrates were degreased with solvent and then treated with oxygen plasma at 50 W and 100 mTorr for 1.5 minutes and UV ozone for 5 minutes.

[0239] OLEDs are manufactured under high vacuum (<10 -6 The devices were fabricated by thermal evaporation at 1000 Å (2000 Å) at 3700 Å (1000 Torr). The anode electrode was 750 Å of indium tin oxide (ITO). The device examples had organic layers consisting of, from the ITO surface, 100 Å of compound 1 (HIL), 250 Å of compound 2 (HTL), 50 Å of compound 3 (EBL), 300 Å of compound 3 (50% doped with compound 4 and 12% emitter) (EML), 50 Å of compound 4 (BL), 300 Å of compound 5 (35% doped with compound 6) (ETL), 10 Å of compound 5 (EIL), and 1,000 Å of Al (cathode). All devices were immediately encapsulated with a moisture getter packaged in a nitrogen glove box (<1 ppm HO and O) and a glass lid sealed with epoxy resin. The doping percentages are the deposition percentages. Table 1: OLED performance summary [Table 1] JPEG0007799418000192.jpg228152JPEG0007799418000193.jpg45152

[0240] The compounds used in the device are as follows: [ka]

[0241] This application discloses platinum N-heterocyclic carbene (NHC) complexes featuring a carbene-N substituent attached or "strapped" to the back portion of the NHC. The strapping of the carbene-N substituent results in significantly improved photophysical properties and device performance over comparable compounds in which the carbene-N phenyl substituent is not strapped to the carbene. In most cases, the spectral shape is much narrower for the strapped NHC than for the comparable compounds, allowing for improved color purity. Generally, the FWHM of the emission spectra of phosphorescent emitter complexes is broad, typically exceeding 50 nm, as shown in the comparative examples herein. Achieving a narrow FWHM has been a long-sought goal. The narrower the FWHM, the better the color purity for display applications. In past OLED research, narrowing of the line shape has been achieved only modestly on the order of nanometers. As seen here, the present compounds with strapping can significantly reduce the FWHM to less than 40 nm, or even to 30 nm. The compounds of the present invention also exhibit a more desirable blue shift, enabling devices with purer colors and greater efficiency. Another notable improvement is that the strapping compounds improve device efficiency by approximately two-fold in almost all examples. Such an improvement is considered very large and represents an important step toward commercialization of these inventive emitters. The significant performance improvement seen in the data above was unexpected, based on the fact that the example compounds of the present invention (Emitter 2, Emitter 3, Emitter 4, Emitter 5, Emitter 6, Emitter 7, and Emitter 13) have similar structures to the comparative compounds, differing only in the additional strapping moiety.

Claims

1. A compound represented by the following formula III or IV: 【Chemistry 1】 (Wherein, ring A is independently a 5- to 10-membered heterocycle; X １ ~X ３ are C and X, respectively. ４ ~X ６ are each independently C or N; R Ａ represents up to the maximum number of possible substitutions for the di or its associated ring; R Ｂ , and X ４ ~X ６ R in a ring containing Ｃ each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R １ , R Ａ , R Ｂ , and X ４ ~X ６ R in a ring containing Ｃ are each independently a substituent selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; At least two adjacent R Ａ the substituents are bonded to form a fused ring to ring A; M １ is Pt; Moieties C and D are each independently a monocyclic or polycyclic structure containing 5- and / or 6-membered carbocyclic or heterocyclic rings; Z １ and Z ２ are each independently C or N; K ３ is a direct bond, O, or S; K １ , and K ２ are each a direct bond; L １ , and L ２ are each independently a direct bond, BR, BRR, NR, PR, O, S, Se, C═O, S═O, or SO ２ , CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, and combinations thereof; n1 and n2 are each 1, and n3 is 0; X ７ ~X ９ are each independently C or N; R in part C Ｃ , and R Ｄ each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R in part C Ｃ , and R Ｄ are each independently a substituent selected from the group consisting of hydrogen or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; R Ａ and R in part C Ｃ Any two adjacent R Ａ , R Ｂ , X ４ ~X ６ R in a ring containing Ｃ , R in part C Ｃ , R Ｄ , or R １ can be bonded or fused to each other to form a chemically possible ring.)

2. R １ , R Ａ , and R Ｂ is each 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.

3. X ４ ~X ６ and each are C.

4. Ring A is a 7-, 8-, 9-, or 10-membered ring, and four adjacent R Ａ 2. The compound of claim 1, wherein the substituents are linked to form two fused rings to ring A.

5. Ring A is an 8-membered ring, a 9-membered ring, or a 10-membered ring, and a total of six adjacent R Ａ 2. The compound of claim 1, wherein the substituents are linked to form three separate rings that are all fused to ring A.

6. The compound according to claim 1, wherein both moieties C and D are six-membered aromatic rings, or moiety C is a five- or six-membered heterocycle.

7. K ３ The compound of claim 1 , wherein is a direct bond.

8. L １ The compound of claim 1, wherein is O, SiRR', or CRR'.

9. L ２ The compound of claim 1 , wherein is a direct bond or NR.

10. 10. The compound of claim 1 having the following structure: 【Chemistry 2】 (In the formula, Z ３ is C or N; Any two adjacent Rs other than the combination of R A and R C in part C Ａ , R Ｂ , R C in the ring containing X 4 to X 6 , R in the portion C Ｃ , R Ｄ , or R １ can be bonded or fused to each other to form a chemically possible ring.)

11. 11. The compound of claim 10 selected from the group consisting of: 【Transformation 3】 【change】 【change】 (In the formula, R ｘ and R ｙ are each selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; R Ｇ are each 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.

12. 10. The compound of claim 1 having the following structure: 【Chemistry 4】 (In the formula, L Ａ’ Is, L Ａ’ 1-(Rs)(Rt)(Ru),L Ａ’ 2-(Rs)(Rt)(Ru),L Ａ’ 3-(Rs)(Rt)(Ru),L Ａ’ 4-(Rs)(Rt)(Ru), L Ａ’ 5-(Rs)(Rt)(Ru), L Ａ’ 6-(Rs)(Rt)(Ru),L Ａ’ 7-(Rs)(Rt)(Ru),L Ａ’ 8-(Rs)(Rt)(Ru), and L Ａ’ 9-(Rs)(Rt)(Ru), wherein s, t, and u are each independently an integer from 1 to 87; 【Transformation 5】 In the ceremony, L Ａ’’ Is, L Ａ’’ 1-(Rs)(Rt)(Ru),L Ａ’’ 2-(Rs)(Rt)(Ru),L Ａ’’ 3-(Rs)(Rt)(Ru),L Ａ’’ 4-(Rs)(Rt)(Ru), L Ａ’’ 5-(Rs)(Rt)(Ru), L Ａ’’ 6-(Rs)(Rt)(Ru),L Ａ’’ 7-(Rs)(Rt)(Ru),L Ａ’’ 8-(Rs)(Rt)(Ru),L Ａ’’ 9-(Rs)(Rt)(Ru),L Ａ’’ 10-(Rs)(Rt)(Ru),L Ａ’’ 11-(Rs)(Rt)(Ru),L Ａ’’ 12-(Rs)(Rt)(Ru),L Ａ’’ 13-(Rs)(Rt)(Ru), L Ａ’’ 14-(Rs)(Rt)(Ru), L Ａ’’ 15-(Rs)(Rt)(Ru),L Ａ’’ 16-(Rs)(Rt)(Ru),L Ａ’’ 17-(Rs)(Rt)(Ru),L Ａ’’ 18-(Rs)(Rt)(Ru),L Ａ’’ 19-(Rs)(Rt)(Ru),L Ａ’’ 20-(Rs)(Rt)(Ru),L Ａ’’ 21-(Rs)(Rt)(Ru),L Ａ’’ 22-(Rs)(Rt)(Ru),L Ａ’’ 23-(Rs)(Rt)(Ru), and L Ａ’’ 24-(Rs)(Rt)(Ru), wherein s, t, and u are each independently an integer from 1 to 87; 【Transformation 6】 【change】 【change】 In the formula, ligand L Ｙ is L Ｙ 1-(Rs)(Rt)(Ru), L Ｙ 2-(Rs)(Rt)(Ru), L Ｙ 3-(Rs)(Rt)(Ru), L Ｙ 4-(Rs)(Rt)(Ru), L Ｙ 5-(Rs)(Rt)(Ru), L Ｙ 6-(Rs)(Rt)(Ru), L Ｙ 7-(Rs)(Rt)(Ru), L Ｙ 8-(Rs)(Rt)(Ru), L Ｙ 9-(Rs)(Rt)(Ru), L Ｙ 10-(Rs)(Rt)(Ru), L Ｙ 11-(Rs)(Rt)(Ru), L Ｙ 12-(Rs)(Rt)(Ru), L Ｙ 13-(Rs)(Rt)(Ru), L Ｙ 14-(Rs)(Rt)(Ru), L Ｙ 15-(Rs)(Rt)(Ru), L Ｙ 16-(Rs)(Rt)(Ru), L Ｙ 17-(Rs)(Rt)(Ru), L Ｙ 18-(Rs)(Rt)(Ru), L Ｙ 19-(Rs)(Rt)(Ru), L Ｙ 20-(Rs)(Rt)(Ru), L Ｙ 21-(Rs)(Rt)(Ru), L Ｙ 22-(Rs)(Rt)(Ru), L Ｙ 23-(Rs)(Rt)(Ru), L Ｙ 24-(Rs)(Rt)(Ru), L Ｙ 25-(Rs)(Rt)(Ru), L Ｙ 26-(Rs)(Rt)(Ru), L Ｙ 27-(Rs)(Rt)(Ru), L Ｙ 28-(Rs)(Rt)(Ru), L Ｙ 29-(Rs)(Rt)(Ru), L Ｙ 30-(Rs)(Rt)(Ru), L Ｙ 31-(Rs)(Rt)(Ru), L Ｙ 32-(Rs)(Rt)(Ru), L Ｙ 33-(Rs)(Rt)(Ru), wherein s, t, and u are each independently an integer from 1 to 87; 【Transformation 7】 【change】 【change】 In the formula, R1 to R87 have the following structure: 【Transformation 8】 【change】 【change】

13. The compound of claim 1 selected from the group consisting of: 【Chemistry 9】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】

14. An organic light emitting device (OLED), comprising: an anode; a cathode; an organic layer disposed between the anode and the cathode; The organic light-emitting device (OLED) is characterized in that the organic layer comprises a compound represented by the following formula III or IV: 【Chemistry 10】 (Wherein, ring A is independently a 5- to 10-membered heterocycle; X １ ~X ３ are C and X, respectively. ４ ~X ６ are each independently C or N; R Ａ represents up to the maximum number of possible substitutions for the di or its associated ring; R Ｂ , and X ４ ~X ６ R in a ring containing Ｃ each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R １ , R Ａ , R Ｂ , and X ４ ~X ６ R in a ring containing Ｃ are each independently a substituent selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; At least two adjacent R Ａ the substituents are bonded to form a fused ring to ring A; M １ is Pt; Moieties C and D are each independently a monocyclic or polycyclic structure containing 5- and / or 6-membered carbocyclic or heterocyclic rings; Z １ and Z ２ are each independently C or N; K ３ is a direct bond, O, or S; K １ , and K ２ are each a direct bond; L １ , and L ２ are each independently a direct bond, BR, BRR, NR, PR, O, S, Se, C═O, S═O, or SO ２ , CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, and combinations thereof; n1 and n2 are each 1, and n3 is 0; X ７ ~X ９ are each independently C or N; R in part C Ｃ , and R Ｄ each independently represents zero, mono, or up to the maximum number of possible substitutions for its associated ring; R in part C Ｃ , and R Ｄ are each independently a substituent selected from the group consisting of hydrogen or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; R Ａ and R in part C Ｃ Any two adjacent R Ａ , R Ｂ , X ４ ~X ６ R in a ring containing Ｃ , R in part C Ｃ , R Ｄ , or R １ can be bonded or fused to each other to form a chemically possible ring.)

Images