Organic electroluminescent materials and devices

Abstract

The present invention provides organometallic compounds, as well as OLEDs and related consumer products that utilize these organometallic compounds. [Solution] The following ligand L A Organometallic compounds containing the following are provided. TIFF2026065028000224.tif62170 Said ligand L A It forms a complex with metal M via two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; the ligand L A It can combine with other ligands to form tridentate, quadridentate, quindentate, or hexadentate ligands.

Description

[Technical Field]

[0001] This application claims priority to U.S. Provisional Application No. 63 / 087,062 filed 2 October 2020 and U.S. Provisional Application No. 63 / 193,755 filed 27 May 2021, pursuant to Section 119(e) of the U.S. Patent Act. The entirety of the disclosures of both of these applications are incorporated herein by reference.

[0002] This disclosure generally relates to organometallic compounds and compositions, as well as various uses thereof, including light-emitting materials in devices such as organic light-emitting diodes and related electronic devices. [Background technology]

[0003] Optoelectronic devices utilizing organic materials are becoming increasingly desirable for various reasons. Since many of the materials used to fabricate such devices are relatively inexpensive, organic optoelectronic devices have the potential to offer a cost advantage over inorganic devices. In addition, due to the inherent properties of organic materials, such as flexibility, they can be well-suited for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photocells, and organic photodetectors. For OLEDs, organic materials may offer performance advantages over conventional materials.

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

[0005] One use of the phosphorescent molecule is a full-color display. The industry standard for such displays requires pixels adapted to emit specific colors called "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. Conventional liquid crystal display emission from a white backlight is filtered using absorption filters to produce red, green, and blue emissions. Similar techniques can also be used with OLEDs. The white OLED can be either a single-layer emissive layer (EML) device or a stacked structure. Color can be measured using CIE coordinates well known in the art.

Summary of the Invention

[0006] In one aspect, the present disclosure provides:

Chemical Formula

[0007] In another embodiment, this disclosure relates to ligand L of formula I or formula II as described herein. A The present invention provides a compound composition containing the following:

[0008] In yet another embodiment, the disclosure relates to ligand L of formula I or formula II as described herein. A The present invention provides an OLED having an organic layer containing a compound including the above.

[0009] In yet another embodiment, the disclosure relates to ligand L of formula I or formula II as described herein. A The present invention provides a consumer product including an OLED having an organic layer containing a compound. [Brief explanation of the drawing]

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

[0011] [Figure 2] Figure 2 shows an inverted organic light-emitting device that does not have another electron transport layer. [Modes for carrying out the invention]

[0012] A. Terminology Unless otherwise specified, the following terms used in this specification are defined as follows:

[0013] As used herein, the term “organic” includes polymeric and low-molecular-weight organic materials that can be used to fabricate organic optoelectronic devices. “Low-molecular-weight” refers to any organic material that is not a polymer, and “low-molecular-weight” can actually be quite large. Low-molecular-weight may include repeating units in some contexts. For example, using long-chain alkyl groups as substituents does not exclude molecules from the “low-molecular-weight” class. Low-molecular-weight may be incorporated into polymers, for example, as pendant groups on a polymer backbone, or as part of said backbone. Low-molecular-weight may also serve as the core portion of a dendrimer, which consists of a series of chemical shells constructed on a core portion. The core portion of a dendrimer may be a fluorescent or phosphorescent low-molecular-weight emitter. Dendrimers can also be “low-molecular-weight,” and all dendrimers currently used in the field of OLEDs are considered to be low-molecular-weight.

[0014] In this specification, “top” means the part furthest from the substrate, while “bottom” means the part closest to the substrate. When it is stated that the first layer is “placed on top of” the second layer, the first layer is located 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 “placed on top of” the anode, even if there are various organic layers in between.

[0015] As used herein, “solution processable” means that it can be dissolved, dispersed or transported in any liquid medium, either in solution or suspension form, and / or deposited from said medium.

[0016] A ligand may be referred to as "photoactive" if it is considered to directly contribute to the photoactive properties of the light-emitting material. A ligand may be referred to as "auxiliary" if it is not considered to contribute to the photoactive properties of the light-emitting material, although auxiliary ligands can alter the properties of photoactive ligands.

[0017] As used herein, as will be generally understood by those skilled in the art, the first “highest occupied molecular orbital” (HOMO) or “lowest empty molecular orbital” (LUMO) energy level is “greater than” or “higher than” the second HOMO or LUMO energy level, if the first energy level is close to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. “Higher” HOMO or LUMO energy levels appear to be closer to the top of such a diagram than “lower” HOMO or LUMO energy levels.

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

[0019] The terms "halo," "halogen," and "halide" are interchangeable 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)-O-R s ) group.

[0022] The term "ether" refers to -OR s group.

[0023] The terms "sulfanyl" or "thioether" are used interchangeably and refer to -SR s group.

[0024] The term "selenyl" refers to SeR s group.

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

[0026] The term "sulfonyl" refers to -SO2-R s group.

[0027] The term "phosphino" refers to -P(R s )3 group, where each R s may be the same or different.

[0028] The term "silyl" refers to -Si(R s )3 group, where each R s may be the same or different.

[0029] The term "germyl" refers to -Ge(R s )3 group, where each R s may be the same or different.

[0030] The term "boryl" refers to -B(R s )2 group, or its Lewis adduct -B(R s )3 group, where R s may be the same or different.

[0031] In each of the above, R sR can be a substituent selected from the group consisting of hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R s The group is selected from alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0032] The term "alkyl" refers to and includes both linear and branched alkyl groups. Preferred alkyl groups contain 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. Furthermore, 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, and adamantyl. Furthermore, the cycloalkyl groups may be optionally substituted.

[0034] The terms "heteroalkyl" and "heterocycloalkyl" refer, respectively, to alkyl or cycloalkyl groups having at least one carbon atom substituted with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Furthermore, the heteroalkyl group or heterocycloalkyl group may be optionally substituted.

[0035] The term "alkenyl" refers to and includes both linear and branched 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 substituted 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 contain 2 to 15 carbon atoms. Furthermore, the alkenyl, cycloalkenyl, or heteroalkenyl groups may optionally be substituted.

[0036] The term "alkynyl" refers to and includes both linear and branched alkyne groups. An alkynyl group is essentially an alkyl group containing at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups contain 2 to 15 carbon atoms. Furthermore, the alkynyl group may be optionally substituted.

[0037] The terms "aralkyl" or "arylalkyl" are interchangeable and refer to alkyl groups substituted with aryl groups. Furthermore, the aralkyl groups 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 can be used interchangeably with heteroaryl groups. Preferred heterononaromatic cyclic groups contain 3 to 7 ring atoms, including at least one heteroatom, and include cyclic amines such as morpholino, piperidino, and pyrrolidino, and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, and tetrahydrothiophene. Furthermore, the heterocyclic group may optionally be substituted.

[0039] The term "aryl" refers to and includes both monocyclic aromatic hydrocarbyl groups and polycyclic aromatic ring systems. Polycyclic means having two or more rings in which two carbon atoms are shared between two adjacent rings (the rings are "condensed"), at least one of which is an aromatic hydrocarbyl group, and the other rings may be, for example, 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 with 6 carbon atoms, 10 carbon atoms, or 12 carbon atoms are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, with phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene being preferred. Furthermore, the aryl groups 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. Examples of heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many examples, O, S, or N are preferred heteroatoms. A heteromonocyclic aromatic ring system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have 1 to 6 heteroatoms. A heteropolycyclic ring system may have two or more rings in which two atoms are common to two adjacent rings (the rings are "condensed"), and at least one of the rings is a heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. A heteropolycyclic aromatic ring system may have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups contain 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, oxathiaidine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, and Examples include nzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzoflopyridine, phlodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, with dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azavolin, 1,3-azavolin, 1,4-azavolin, borazine, and aza-like compounds thereof. Furthermore, the heteroaryl group may be optionally substituted.

[0041] Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, as well as their respective aza-like analogs, are of particular interest.

[0042] The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted or independently substituted with one or more common substituents.

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

[0044] In some examples, preferred common 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 examples, preferred common substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.

[0046] In other examples, 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 substituents other than H that are bonded to the relevant position (e.g., carbon or nitrogen). For example, R 1 If represents a mono-substitution, then one R 1 It must be something other than H (i.e., a substitution). Similarly, R 1 If R represents a di-substitution, 1 These two must be other than H. Similarly, R 1 If R represents zero or no substitution,1 This can be hydrogen in the available valence of a ring atom, such as the carbon atom in benzene and the nitrogen atom in pyrrole, or it simply represents nothing in the case of a ring atom with a fully filled valence (e.g., nitrogen in pyridine). The maximum number of possible substitutions in a ring structure depends on the total number of available valences in the ring atom.

[0048] Where used herein, “these combinations” means that one or more members of the applicable list are combined to form known or chemically stable configurations that can be conceived by those skilled in the art 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 an alkyl halide substituent; halogen, alkyl, and aryl can be combined to form an arylalkyl halide. In one example, the term substitution includes combinations of two to four of the listed groups. In another example, the term substitution includes combinations of two to three groups. In yet another example, the term substitution includes combinations of two groups. Preferred substitution combinations include those containing up to 50 atoms that are not hydrogen or deuterium, or up to 40 atoms that are not hydrogen or deuterium, or up to 30 atoms that are not hydrogen or deuterium. In many examples, preferred substitution combinations include up to 20 atoms that are not hydrogen or deuterium.

[0049] In this specification, the name "aza" in fragments such as aza-dibenzofuran and aza-dibenzothiophene means that one or more CH groups in each aromatic ring can be replaced by nitrogen atoms. For example, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline, without limitation. Those skilled in the art will readily be able to imagine other nitrogen analogues of the aza derivatives described above, and all such analogues are intended to be encompassed by the terms used 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. Patent No. 8,557,400, International Publication No. WO2006 / 095951, and U.S. Patent Application Publication No. 2011 / 0037057, which are incorporated herein by reference in their entireties, describe the preparation of organometallic complexes substituted with deuterium. Further references are made by Tetrahedron 2015, 71, 1425 - 30 (Ming Yan et al.) and Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744 - 65 (Atzrodt et al.), which are incorporated herein by reference in their entireties, and describe an efficient route for deuterating methylene hydrogens in benzylamine and substituting aromatic ring hydrogens with deuterium, respectively.

[0051] It should be understood that when a molecular fragment is described as a substituent or as being attached to another moiety, its name may be described as a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). In this specification, these are considered to be equivalent even if the ways of representing substituents or linking fragments are different.

[0052] In one example, a pair of adjacent substituents may optionally bond or condense to form a ring. Preferred rings are 5 - membered, 6 - membered, or 7 - membered carbocyclic or heterocyclic rings, including both examples where the ring portion formed by the pair of substituents is saturated and examples where the ring portion formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that as long as a stable fused - ring system can be formed, two relevant substituents can be adjacent to each other on the same ring or on two adjacent rings having the two closest available substitutable positions, such as the 2 - position and 2'- position in biphenyl and the 1 - position and 8 - position in naphthalene.

[0053] B. Compounds of the present disclosure In one embodiment, this disclosure is as follows: [ka] ligand L A The present invention provides a compound comprising, in the formula, ring A independently being a 5-membered to 10-membered heteroring; X 1 ~X 6 Each is independently either C or N; K 3 The direct bond is O or S; the maximum number of N atoms bonded to each other in the ring is 2; R A , R B , and R C Each independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R1, R A , R B , R C Each of these substituents is independently selected from the group consisting of hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, gelmyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphinol, and combinations thereof, and the ligand L A It complexes with metal M via two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; the ligand L A It can combine with other ligands to form tridentate, quadrupate, quintate, sextate, or heptate ligands; any two adjacent R A , R B , R C , or R1 is the compound described below: [ka] They can bond or condense to form a ring, provided that neither of the structures shown is included.

[0054] In some embodiments, R1, R A , and R B Each of these substituents can be independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanil, and combinations thereof.

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

[0056] In some embodiments, two adjacent R A Substituents can bond to ring A to form a fused ring. In some embodiments, when ring A is a 7-membered, 8-membered, 9-membered, or 10-membered ring, four adjacent R A Substituents can bond to ring A to form two fused rings. In some embodiments, when ring A is an 8-membered, 9-membered, or 10-membered ring, a total of six adjacent R ASubstituents can bond to form three separate rings, all of which condense with ring A. In some embodiments, each fused ring can be independently a five-membered or six-membered aromatic ring. In some embodiments, each fused ring can be independently benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole. In some embodiments, each fused ring can be independently benzene or imidazole. In some embodiments, all fused rings can be benzene.

[0057] In some embodiments, one R1 substituent of formula I and one R B Substituents can bond to form a ring. In some embodiments, one R1 substituent of formula I and one R A Substituents can bond to form a ring. In some embodiments, one R of formula II C substituent and one R B Substituents can bond to form a ring. In some embodiments, one R of formula II C substituent and one R A A substituent can bond to form a ring. In some embodiments, two adjacent R B Substituents can bond to form a fused ring. In some embodiments, two adjacent R C Substituents can bond to form a fused ring.

[0058] In some embodiments, ligand L A The following group can be selected: [ka] In the formula, ring A1 is independently a 5-membered to 10-membered heteroring; rings A2, A3, A4, A5, B2, and B3 are independently a 5-membered or 6-membered carbon ring or heteroring; and ring B1 is independently a 5-membered, 6-membered, or 7-membered carbon ring or heteroring.

[0059] In some embodiments, ligand L A can be selected from the group consisting of the following.

Chemical formula

[0060] In some embodiments, ligand L A is as follows:

Chemical formula

Chemical formula

Chemical formula

[0061] In some embodiments, ligand 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), LA 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 The set can be selected from the group consisting of 32-(Rs)(Rt)(Ru), where s, t, and u are each independent integers from 1 to 87, and where, [ka] TIFF2026065028000013.tif215170 TIFF2026065028000014.tif213170 In formula TIFF2026065028000015.tif131170, R1 to R87 have the following structure: [ka] TIFF2026065028000017.tif228170 TIFF2026065028000018.tif163170

[0062] In some embodiments, the compound is of formula M(L A ) p (L B ) q (L C ) r It can have, in the formula, L B and L C A, b, and r are bidentate ligands; 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 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 The formula may be selected from the group consisting of ), where L A , L B , and L C They are different from each other.

[0064] In some embodiments, the compound is of the formula Pt(L A )(L B ) can have, in the formula, L A and L B L may be the same or different. In some embodiments, L A and L BThese can combine to form a tetradentate ligand.

[0065] In some embodiments, L B and L C Each of these can be independently selected from the following group: [ka] During the ceremony, T is selected from the group consisting of B, Al, Ga, and In; Y 1 ~Y 13 Each is independently selected from the group consisting of carbon and nitrogen; Y' is BR e , NR e PR e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f Selected from the group consisting of; R e and R f They can condense or bond to form a ring; Each R a , R b , R c , and R d It independently represents zero, mono, or the maximum number of possible permutations on its associated ring; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e , and R fEach of these is independently a substituent selected from the group consisting of hydrogen, or deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, gelmyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphinol, and combinations thereof; and common substituents described herein; Any two adjacent R a , R b , R c , R d , R e , and R f These can condense or bond to form rings or polydentate ligands.

[0066] In some embodiments, L B and L C Each of these can be independently selected from the following group: [ka] TIFF2026065028000021.tif221170 TIFF2026065028000022.tif123170 R a ', R b ', and R c Each of these independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R a1 , R b1 , R c1 , R a , R b , R c , R N , R a ', R b ', and R cEach of these substituents is independently selected from the group consisting of hydrogen, or deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, gelmyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphine, and combinations thereof; Any two adjacent R a ', R b ', and R c These elements can condense or bond to form rings or polydentate ligands.

[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 You can choose from the group consisting of ), In the formula, L A is a ligand as described herein; k is an integer from 1 to 324, and each L Bk This is defined in List 2 below. [ka] TIFF2026065028000024.tif231170 TIFF2026065028000025.tif229170 TIFF2026065028000026.tif230170 TIFF2026065028000027.tif222170 TIFF2026065028000028.tif237170 TIFF2026065028000029.tif212170 TIFF2026065028000030.tif246170 TIFF2026065028000031.tif246170 TIFF2026065028000032.tif247170 In formula TIFF2026065028000033.tif55170, n is an integer from 1 to 180, and each L BBn This is defined in List 3 below. [ka] TIFF2026065028000035.tif213170 TIFF2026065028000036.tif211170 TIFF2026065028000037.tif246170 TIFF2026065028000038.tif214170 TIFF2026065028000039.tif233170 TIFF2026065028000040.tif221170 TIFF2026065028000041.tif47170, each L Cj-I The formula is: [ka] It has a structure based on each L Cj-II The formula is: [ka] It has a structure based on, In the formula, L Cj-I and L Cj-II Each L in Cj Regarding R 201 and R 202 These are defined independently in List 4 below. [ka] TIFF2026065028000045.tif247170 TIFF2026065028000046.tif247170 TIFF2026065028000047.tif247170 TIFF2026065028000048.tif246170 TIFF2026065028000049.tif247170 TIFF2026065028000050.tif246170 TIFF2026065028000051.tif247170 TIFF2026065028000052.tif247170 TIFF2026065028000053.tif247170 TIFF2026065028000054.tif205170, R D1 ~R D246 It has the following structure: [ka] TIFF2026065028000056.tif229170 TIFF2026065028000057.tif246170 TIFF2026065028000058.tif237170 TIFF2026065028000059.tif121170

[0068] In some embodiments, the compound is of 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 ) can have, and the compound is L Bkor L BBn As the ligand, it consists of only one of the following structures: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B130 , L B132 , L B134 , L B136 , L B138 , L B140 , L B142 , L B144 , L B156 , L B158 , L B160 , L B162 , L B164 , L B168 , L B172 , L B175 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B222 , L B231 , L B233 , L B235 , L B237 , L B240 , L B242 , L B244 , L B246 , L B248 [[ID=...]] , L B250 , L B252 , L B254 , L B256 , L B258 , L B260 , L B262 and L B264 , L B265 , L B266 , L B267 , L B268 , L B269 , L B270 , L BB1 , L BB2 , L BB3 , L BB4 , L BB5 , L BB6 , L BB7 , LBB8 , L BB9 , L BB10 , L BB11 , L BB2 , L BB13 , L BB14 , L BB15 , L BB16 , L BB17 , L BB18 , L BB20 , L BB22 , L BB24 , L BB34 , L BB37 , L BB71 , L BB74 , L BB88 , L BB90 , L BB97 , L BB103 , L BB104 , L BB105 , L BB106 , L BB107 , L BB112 , L BB113 , L BB115 , L BB116 , L BB117 , L BB118 , L BB119 , L BB121 , L BB122 , and L BB123 .

[0069] In some embodiments, the compound is of 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 ) can have, and the compound is L Bk or L BBn The ligand consists of only one of the following structures: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B126 , L B128 , L B132 , L B136 , LB138 , L B142 , L B156 , L B162 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B231 , L B233 , L B237 , L B264 , L B265 , L B266 , L B267 , L B268 , L B269 , 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 ) can have ligand L Cj-I and L Cj-II As such, the compounds are their corresponding R 201 and R 202 However, L is defined to be one of the following structures. Cj-I and L Cj-II Includes ligands only: 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 is of the formula Ir(L A )2(L Cj-I) or Ir(L A )2(L Cj-II ) can have ligand L Cj-I and L Cj-II As such, the compounds are their corresponding R 201 and R 202 However, L is defined to be one of the following structures. Cj-I and L Cj-II Includes ligands only: R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D22 , R D43 , R D50 , R D78 , R D116 , R D118 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D149 , R D151 , R D154 , R D155 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 .

[0072] In some embodiments, the compound is of the formula Ir(L A )2(L Cj-I ) can have, and the compound is L Cj-I The ligand consists of only one of the following structures. [ka]

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

[0074] In some embodiments, the compound may have the following structure. [ka] During the ceremony, M 1 is either Pd or Pt; Parts C and D are independently monocyclic or polycyclic structures containing five-membered and / or six-membered carbon rings or heterocyclic rings; Z 1 and Z 2 Each of these is independently either C or N; K 1 , K 2 , and K 3 Each is independently selected from direct bond, O, and S, and K 1 , K 2 , or K 3 At least two of them are direct connections; L 1 , L 2 , and L 3 Each is independently selected from the group consisting of direct bonds, BR, BRR, NR, PR, O, S, Se, C=O, S=O, SO2, C=CRR', CRR', SiRR', GeRR', alkyl, cycloalkyl, and combinations thereof, L 1 and L 2 At least one of the following exists; n1, n2, and n3 are either 0 or 1, and n1+n2+n3=2 or 3; X 7 ~X 9 Each of these is independently either C or N; RC and R D Each independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R C and R D Each of these substituents is independently 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; Any two adjacent R A , R B , R C , R D , or R1 can bond or condense with each other to form a chemically possible ring; and X 1 ~X 6 , R A , R B The definitions of ring A and ring A are the same as those described above.

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

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

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

[0078] In some embodiments, K 1 , K2 , and K 3 Each of these can be a direct bond. In some embodiments, K 1 , K 2 , or K 3 Any of these can be O. In some embodiments, K 1 or K 2 Any of these can be O. In some embodiments, K 3 It can be O.

[0079] In some embodiments, X 7 ~X 9 All of these can be C.

[0080] In some embodiments, the compound may have the following structure. [ka] In the formula, Z 3 is C or N; the remaining variable part is the same as the definition above; any two adjacent R A , R B , R C , R D Alternatively, R1 can bond or condense with each other to form a ring.

[0081] In some embodiments of formula V or formula VI, R1, R A , and R B Each of these substituents can be independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanil, and combinations thereof.

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

[0083] In some embodiments, two adjacent R A Substituents can bond to ring A to form a fused ring. In some embodiments, when ring A is a 7-membered, 8-membered, 9-membered, or 10-membered ring, two further adjacent R A Substituents can bond to ring A to form a further fused ring. In some embodiments, a total of six adjacent R A Substituents can bond to form three separate rings, all of which condense with ring A. In some embodiments, all fused rings can be five-membered or six-membered aromatic rings. In some embodiments, each fused ring can independently be benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole. In some embodiments, each fused ring can be benzene.

[0084] In some embodiments, one R1 substituent and one R B Substituents can bond to form a ring. In some embodiments, one R1 substituent of formula V and one R A A substituent can bond to form a ring. In some embodiments, one R of formula VI C substituent and one R B A substituent can bond to form a ring. In some embodiments, one R of formula VI C substituent and one R A A substituent can bond to form a ring. In some embodiments, two adjacent R B Substituents can bond to form a fused ring. In some embodiments, two adjacent R C Substituents can bond to form a fused ring.

[0085] In some embodiments, ring C and ring D can each be independently 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] TIFF2026065028000065.tif205170 TIFF2026065028000066.tif154170, R x and R y Each is selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; R G Each of these substituents is independently 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; X 1 ~X 6 , R1, R A , R B , R C , R E , R F , L 1 The definitions of ring A and ring A are the same as those described above.

[0087] In some embodiments, the compound may 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’ Selected from the group consisting of 9-(Rs)(Rt)(Ru), where s, t, and u are each independent integers from 1 to 87, [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), 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’’ Selected from the group consisting of 24-(Rs)(Rt)(Ru), where s, t, and u are each independent integers from 1 to 87, [ka] TIFF2026065028000070.tif237170 TIFF2026065028000071.tif156170 In 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 Y25-(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 The group can be selected from 33-(Rs)(Rt)(Ru), where s, t, and u are each independent integers from 1 to 87, and in the formula, [ka] TIFF2026065028000073.tif232170 In formula TIFF2026065028000074.tif252170, R1 to R87 have the following structure. [ka] TIFF2026065028000076.tif213170 TIFF2026065028000077.tif87170

[0088] In some embodiments, the compound can be selected from the group defined in the following List 9. [ka] TIFF2026065028000079.tif214170 TIFF2026065028000080.tif212170 TIFF2026065028000081.tif247170 TIFF2026065028000082.tif240170 TIFF2026065028000083.tif221170 TIFF2026065028000084.tif224170 TIFF2026065028000085.tif197170 TIFF2026065028000086.tif247170 TIFF2026065028000087.tif237170 TIFF2026065028000088.tif222170 TIFF2026065028000089.tif212170 TIFF2026065028000090.tif224170 TIFF2026065028000091.tif138170

[0089] In some embodiments, the compound can be selected from the group consisting of the following structures. [ka] TIFF2026065028000093.tif195170 TIFF2026065028000094.tif223170 TIFF2026065028000095.tif180170 TIFF2026065028000096.tif79170

[0090] In some embodiments, ligand L of formula I or formula II as described herein ACompounds having can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. In this specification, the deuterated percentage (%) has its usual meaning and includes the percentage (%) of hydrogen atoms that can be substituted by deuterium atoms (e.g., the position of hydrogen, deuterium, or halogen).

[0091] In some embodiments, ligand L of formula I or formula II as described herein A Compounds having can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. In this specification, the deuterated percentage (%) has its usual meaning and includes the percentage (%) of hydrogen atoms that can be substituted by deuterium atoms (e.g., the position of hydrogen, deuterium, or halogen).

[0092] C. OLEDs and devices of this disclosure In another embodiment, the Disclosure also provides an OLED device comprising a first organic layer containing a compound disclosed in the aforementioned Compounds section of the Disclosure.

[0093] In some embodiments, the organic layer is as follows: [ka] ligand L A Compounds containing can include, where ring A is independently a 5-membered to 10-membered heterocycle; X 1 ~X 6Each is independently either C or N; K 3 The direct bond is O or S; the maximum number of N atoms bonded to each other in the ring is 2; R A , R B , and R C Each independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R1, R A , R B , R C Each of these is independently a substituent selected from the group consisting of hydrogen or general substituents as defined herein, and the ligand L A It complexes with metal M via two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; the ligand L A It can combine with other ligands to form tridentate, quadrupate, quintate, sextate, or heptate ligands; any two adjacent R A , R B , R C , or R1 is the compound described above, which is: [ka] They can bond or condense to form a ring, provided that neither of the structures shown is included.

[0094] In some embodiments, the organic layer may be a light-emitting layer, and the compounds described herein may be light-emitting dopants or non-light-emitting dopants.

[0095] In some embodiments, the organic layer may further include a host, the host comprising a triphenylene containing a benzo-condensed thiophene or a benzo-condensed furan, and any substituent in the host independently being C n H 2n+1 , OC n H 2n+1 ,OAr1,N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H2n+1 , C≡CC n H 2n+1 Ar1, Ar1-Ar2, C n H 2n -Ar1 is a non-condensed substituent selected from the group consisting of Ar1, and can be unsubstituted, with n being 1 to 10, and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and their heteroaromatic analogs.

[0096] In some embodiments, the organic layer may further include a host, the host comprising at least one chemical moiety selected from the group consisting of naphthalene, fluorene, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-naphthalene, aza-fluorene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

[0097] In some embodiments, the host can be selected from a group selected from the following: [ka] TIFF2026065028000100.tif222170 TIFF2026065028000101.tif163170

[0098] In some embodiments, the organic layer may further include a host, the host of which includes a metal complex.

[0099] In some embodiments, the compounds described herein may be sensitizers, and the device may further include an acceptor, the acceptor may 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 may also include a light-emitting region comprising a compound disclosed in the aforementioned compound section of the present disclosure.

[0101] In some embodiments, the light-emitting region is as follows: [ka] ligand L A Compounds containing can include, where ring A is independently a 5-membered to 10-membered heterocycle; X 1 ~X 6 Each is independently either C or N; K 3 The direct bond is O or S; the maximum number of N atoms bonded to each other in the ring is 2; R A , R B , and R C Each independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R1, R A , R B , R C Each of these is independently a substituent selected from the group consisting of hydrogen or general substituents as defined herein, and the ligand L A The ligand L forms a complex with metal M via two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; the ligand L A It can combine with other ligands to form tridentate, quadrupate, quintate, sextate, or heptate ligands; any two adjacent R A , R B , R C , or R1 is the compound described above, which is: [ka] They can bond or condense to form a ring, provided that neither of the structures shown is included.

[0102] In some embodiments, at least one of the anode, cathode, or new layer placed on top of the organic light-emitting layer functions as an enhancement layer. The enhancement layer includes a plasmon material that non-radiatively bonds to the light-emitting material and exhibits surface plasmon resonance, transferring excited state energy from the light-emitting material to non-radiative mode surface plasmon polaritons. The enhancement layer is located within a threshold distance from the organic light-emitting layer, and the light-emitting material has a total non-radiative decay rate constant and a total radioactive decay rate constant in the presence of the enhancement layer, where, at the threshold distance, the total non-radiative decay rate constant is equal to the total radioactive decay rate constant. In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is located on top of the enhancement layer opposite the organic light-emitting layer. In some embodiments, the outcoupling layer is located on the opposite side of the light-emitting layer from the enhancement layer, but still outcouples energy from the surface plasmon modes of the enhancement layer. The outcoupling layer scatters energy from 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 to other modes of the device, such as organic waveguide modes, substrate modes, or other waveguide modes, etc. If the energy is scattered to non-free-space modes of the OLED, other outcoupling schemes can be incorporated to extract that energy into free space. In some embodiments, one or more intervening layers can be placed between the enhancement layer and the outcoupling layer. Examples of intervening layers can be dielectric materials including organic, inorganic, perovskite, and oxide materials, and may include laminates and / or mixtures of these materials.

[0103] An enhancement layer alters the effective properties of the medium in which the light-emitting material resides, resulting in one or all of the following: a decrease in luminescence, a change in the shape of the light-emitting line, a change in light-emitting intensity with respect to angle, a change in the stability of the light-emitting material, a change in the efficiency of the OLED, and a decrease in the efficiency roll-off of the OLED device. Placing the enhancement layer on the cathode side, the anode side, or both sides results in an OLED device that takes advantage of any of the aforementioned effects. In addition to the specific functional layers shown in the various OLED examples described and illustrated herein, the OLEDs of this disclosure may include any of the other functional layers commonly found in OLEDs.

[0104] The enhancement layer may consist of a plasmon material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmon material is a material whose real part of dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmon material comprises at least one metal. In such embodiments, the metal may 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 laminates of these materials. Generally, a metamaterial is a medium composed of different materials, where the medium as a whole behaves differently from the sum of its individual material parts. In particular, an optically active metamaterial is defined as a material having both a negative dielectric constant and a negative magnetic permeability. A hyperbolic metamaterial, on the other hand, is an anisotropic medium in which the dielectric constant or magnetic permeability has different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are distinctly different 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 a wavelength scale. Using terminology understandable to those skilled in the art, the dielectric constant of a metamaterial in the direction of propagation can be described by the effective medium approximation. Plasmon and metamaterials provide a way to control the propagation of light and can improve OLED performance in various ways.

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

[0106] In some embodiments, the outcoupling layer has periodically, quasi-periodic, or randomly arranged wavelength-size features, or periodically, quasi-periodic, or randomly arranged sub-wavelength-size features. In some embodiments, the outcoupling layer may consist of a plurality of nanoparticles, and in other embodiments, the outcoupling layer may consist of a plurality of nanoparticles arranged on a material. In these embodiments, the outcoupling may be tunable by at least one of varying the size of the plurality of nanoparticles, varying the shape of the plurality of nanoparticles, varying the material of the plurality of nanoparticles, adjusting the thickness of the material, varying the refractive index of the material or the refractive index of any further layer arranged on the plurality of nanoparticles, varying the thickness of an enhancement layer, and / or varying the material of the enhancement layer. The plurality of nanoparticles in the device may be formed from at least one of metals, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, a laminate 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 laminates of these materials. Multiple nanoparticles may have further layers arranged on top of them. In some embodiments, the polarization of the emission can be tuned using the outcoupling layer. By changing the dimension 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 in the device.

[0107] In yet another embodiment, the Disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound disclosed in the Compounds section of the 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, wherein the organic layer is as follows: [ka] ligand L A Compounds containing can include, where ring A is independently a 5-membered to 10-membered heterocycle; X 1 ~X 6 Each is independently either C or N; K 3 The direct bond is O or S; the maximum number of N atoms bonded to each other in the ring is 2; R A , R B , and R C Each independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R1, R A , R B , R C Each of these is independently a substituent selected from the group consisting of hydrogen or general substituents as defined herein, and the ligand L A The ligand L forms a complex with metal M via two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; the ligand L A It can combine with other ligands to form tridentate, quadrupate, quintate, sextate, or heptate ligands; any two adjacent R A , R B , R C , or R1 is the compound described above, which is: [ka] They can bond or condense to form a ring, provided that neither of the structures shown is included.

[0109] In some embodiments, the consumer product may be one of the following: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signal transmission, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays less than 2 inches diagonally, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays arranged side by side, theater or stadium screens, phototherapy devices, and billboards.

[0110] Generally, an OLED includes at least one organic layer positioned between the anode and cathode and electrically connected to them. When an electric current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons move to the oppositely charged electrodes, respectively. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. Light is emitted via a photoemission mechanism when the exciton relaxes. In some cases, excitons may be localized on an excimer or exciplex. Non-radiative mechanisms such as thermal relaxation may occur, but these are generally considered undesirable.

[0111] Several OLED materials and configurations are described in U.S. Patent Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated in whole by reference.

[0112] Early OLEDs used light-emitting molecules ("fluorescent") that emitted light from their singlet state, as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated in its entirety by reference. Fluorescence emission generally occurs within a timeframe of less than 10 nanoseconds.

[0113] More recently, OLEDs with light-emitting materials ("phosphorescent") that emit light from a triplet state have been demonstrated. See, in their entirety, Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, Vol. 395, pp. 151-154, 1998 ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, No. 3, pp. 4-6 (1999) ("Baldo-II"). Phosphorescence is described in further detail in U.S. Patent No. 7,279,704, paragraphs 5-6, which is incorporated by reference.

[0114] Figure 1 shows an organic light-emitting device 100. The figure is not necessarily to a constant 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, a light-emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of these various layers, as well as examples of materials, are described in further detail in US7,279,704, sections 6-10, which are incorporated by reference.

[0115] Further examples are available for each of these layers. For example, flexible and transparent substrate-anode combinations are disclosed in U.S. Patent No. 5,844,363, which is incorporated in its entirety by reference. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication 2003 / 0230980, which is incorporated in its entirety by reference. Examples of luminescent and host materials are disclosed in Thompson et al., U.S. Patent No. 6,303,238, which is incorporated in its entirety by reference. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication 2003 / 0230980, which is incorporated in its entirety by reference. U.S. Patents 5,703,436 and 5,707,745, which are incorporated in their entirety by reference, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with a transparent, conductive, sputtered-deposited ITO layer covering it. The theory and use of blocking layers are described in more detail in U.S. Patents 6,097,147 and U.S. Patent Application Publication 2003 / 0230980, which are incorporated in their entirety by reference. An example of an injection layer is provided in U.S. Patent Application Publication 2004 / 0174116, which is incorporated in its entirety by reference. A description of a protective layer can be found in U.S. Patent Application Publication 2004 / 0174116, which is incorporated in its entirety by reference.

[0116] Figure 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the described layers in order. The most common OLED configuration has a cathode positioned above the anode, and since device 200 has a cathode 215 positioned below the anode 230, device 200 can be referred to as an "inverted" OLED. The same materials described for device 100 may be used in the corresponding layers of device 200. Figure 2 provides an example of how some layers may be omitted from the structure of device 100.

[0117] The simple layered structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and embodiments of this disclosure may be used in relation to a wide variety of other structures. The specific materials and structures described are factually illustrative, and other materials and structures may be used. Functional OLEDs may be realized 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 containing a single material, it should be understood that combinations of materials, such as host and dopant mixtures, or more generally, mixtures, may be used. Furthermore, layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, the hole transport layer 225 transports holes and injects them into the light-emitting layer 220, and may be described as a hole transport layer or hole injection layer. In one embodiment, the OLED may be described as having an “organic layer” positioned between the cathode and the anode. The organic layer may consist of a single layer or may further consist of multiple layers of different organic materials, for example, as described with respect to Figures 1 and 2.

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

[0119] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal deposition, such as those described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated by reference; inkjet deposition; organic vapor deposition (OVPD), such as those described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated by reference; and organic vapor jet printing (OVJP), such as those described in U.S. Patent No. 7,431,968, which are incorporated by reference. Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal deposition. Preferred patterning methods include those described in U.S. Patents No. 6,294,398 and No. 6,468,819, which are incorporated in whole by reference, as well as patterning related to several deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may be used. The material to be deposited may be modified to suit a particular deposition method. For example, substituents such as alkyl and aryl groups, which are branched or unbranched and preferably contain at least three carbon atoms, may be used in low molecular weight materials to enhance their ability to undergo solution processing. Substituents with 20 or more carbon atoms may be used, with 3 to 20 carbon atoms 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 low molecular weight materials to undergo solution processing.

[0120] Devices fabricated according to embodiments of this 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 on, below, or next to the substrate, electrodes, or on any other part of the device, including edges. The barrier layer may consist of a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include single-phase and multi-phase compositions. 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 polymer and non-polymer materials, as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in whole. For a mixture to be considered a "mixture," the polymer and non-polymer materials, including the barrier layer, should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of the polymer material to the non-polymer material can be in the range of 95:5 to 5:95. The polymer and non-polymer materials may be made from the same precursor material. In one example, the mixture of polymer and non-polymer materials essentially consists of polymer silicon and inorganic silicon.

[0121] Devices fabricated according to embodiments of this 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 and lighting devices (such as discrete light source devices or lighting panels) that can be used by end-user product manufacturers. Such electronic component modules may optionally include drive electronics and / or power supplies. Devices fabricated according to embodiments of this disclosure can be incorporated into a wide variety of consumer products having one or more incorporated electronic component modules (or units). A consumer product is disclosed that includes an OLED in which the organic layer of the OLED contains the compounds of this disclosure. Such a consumer product includes any type of product that includes one or more light sources and / or one or more of the kinds of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signal transmission, head-up displays, fully or partially transparent displays, flexible displays, displays that can be rolled up, displays that can be folded, displays that can be stretched, 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 diagonally), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays arranged together, theater or stadium screens, phototherapy devices, and billboards. Devices manufactured in accordance with this disclosure can be controlled using various control mechanisms, including passive matrices and active matrices. Many of the devices are intended for use within a human-comfortable temperature range, such as 18 to 30 degrees Celsius, more preferably room temperature (20 to 25 degrees Celsius), but can also be used outside this temperature range, for example, -40 to +80 degrees Celsius.

[0122] Further details regarding OLEDs and the definitions used herein can be found in U.S. Patent No. 7,279,704, which is incorporated in its entirety by reference.

[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 these materials and structures. More generally, organic devices such as organic transistors may use these materials and structures.

[0124] In some embodiments, the OLED has one or more properties selected from the group consisting of being flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further includes a layer containing carbon nanotubes.

[0125] In some embodiments, the OLED further includes a layer containing a delayed fluorescence emitter. In some embodiments, the OLED includes 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 an illumination panel.

[0126] In some embodiments, the compound may be a luminescent dopant. In some embodiments, the compound may produce luminescence via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as type E delayed fluorescence; see, for example, U.S. Patent Application No. 15 / 700,352, which is incorporated in whole by reference), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the luminescent dopant may be a racemic mixture or may be enriched with one enantiomer. In some embodiments, the compound may be homoreptic (each ligand is the same). In some embodiments, the compound may be heteroreptic (at least one ligand is different from the others). If there is more than one ligand coordinating to the metal, in some embodiments, these ligands may all be identical. In some other embodiments, at least one ligand is different from the others. In some embodiments, all ligands may be different from each other. This also applies to embodiments in which ligands coordinating to a metal can combine with other ligands coordinating to that metal to form a tridentate, quadrdentate, quindentate, or hexadentate ligand. Therefore, when coordinating ligands are combined with each other, in some embodiments all ligands can be identical, and in some other embodiments at least one of the combined ligands can be different from the others.

[0127] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, and one or more layers in the OLED contain acceptors in the form of one or more fluorescent and / or delayed-fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor, which emits energy or further transfers energy to the final emitter. The acceptor concentration may be in the range of 0.001% to 100%. The acceptor may 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 may arise from any or all of the sensitizer, the acceptor, and the final emitter.

[0128] In other embodiments, compositions comprising the compounds described herein are also disclosed.

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

[0130] Further embodiments of this disclosure describe compositions comprising novel compounds disclosed herein. Such compositions may also comprise one or more components selected from the group consisting of solvents, hosts, hole injection materials, hole transport materials, electron blocking materials, and electron transport materials disclosed herein.

[0131] This disclosure encompasses any chemical structure including the novel compounds of this disclosure or their monovalent or polyvalent variants. In other words, the compounds of the present invention or their monovalent or polyvalent variants may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also known as supermolecules). As used herein, “monovalent variant of a compound” refers to a portion identical to the compound except that one hydrogen atom has been removed and replaced by a bond to the rest of the chemical structure. As used herein, “polyvalent variant of a compound” refers to a portion identical to the compound except that one or more hydrogen atoms have been removed and replaced by bonds to the rest of the chemical structure. In the example of a supramolecule, the inventive compound may also be incorporated into the supramolecular complex without covalent bonding.

[0132] D. Combinations of the compounds disclosed herein with other materials Materials described herein as useful for specific layers in organic light-emitting devices may be used in combination with a wide variety of other materials present in the device. For example, the light-emitting dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other possible layers. The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that may be useful in combination.

[0133] a) Conductive dopants: Charge transport layers are doped with conductive dopants, significantly altering the density of charge carriers and thereby changing their conductivity. Conductivity is increased by generating charge carriers in the matrix material or, depending on the type of dopant, and changes in the Fermi level of the semiconductor can also be achieved. Hole transport layers can be doped with p-type conductive dopants, while n-type conductive dopants are used in electron transport layers.

[0134] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing 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 materials used in this disclosure are not particularly limited, and any compound may be used as long as the compound is typically used as a hole injection / transport material. Examples of materials include: phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorinated hydrocarbons; polymers having conductive dopants; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; and MoO2. x This includes, but is not limited to, metal oxide derivatives such as; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonnitrile; 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 these paragraphs and the entirety of the publication 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 emitted from the light-emitting layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or a longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to restrict light emission to a desired region of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the light-emitting element 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 embodiment, the compound used in the EBL contains the same molecule or the same functional group 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 include 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 greater 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 these paragraphs and the entirety of the publication are incorporated herein by reference.

[0140] e) Additional light-emitting elements: One or more additional luminescent dopants may be used with the compounds of this disclosure. Examples of such additional luminescent dopants are not particularly limited, and any compound can be used as long as the compound is typically used as a luminescent material. Examples of suitable luminescent materials include, but are not limited to, compounds that can generate light through phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as type E delayed fluorescence), triplet-triplet annihilation, or a combination of these processes. Non-limiting examples of light-emitting materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated in paragraphs

[0126] to

[0127] of Universal Display Corporation's U.S. Patent Publication No. 2020 / 0,295,281 A1, the contents of which 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 emitting from the light-emitting layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or a longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to restrict light emission to a desired region of the OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than the light-emitting material closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than one or more hosts closest to the HBL interface.

[0142] In one embodiment, the compound used in the HBL contains the same molecule or the same functional group as the one used in the host described above.

[0143] In another embodiment, the compound used in the HBL contains at least one of the following groups in its molecule. [ka] In the formula, 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: An electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used, as long as it is typically used for electron transport.

[0145] In one embodiment, the compound used in the ETL contains at least one of the following groups in its molecule. [ka] In the formula, R 101 Ar 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, phosphinol, and combinations thereof, and if it is aryl or heteroaryl, it has the same definition as Ar mentioned above. 1 From Ar 3It has the same definition as Ar mentioned above. k is an integer from 1 to 20. X 101 From X 108 This is selected from C (including CH) or N.

[0146] In another embodiment, the metal complex used in the ETL may include, but is not limited to, the following general formulas. [ka] In the formula, (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N, or N, N; L 101 ' is another ligand; k' is an integer value from 1 up to the maximum number of ligands that can bond to the metal. Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated 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 are incorporated herein by reference.

[0147] h) Charge Generation Layer (CGL) In tandem or stacked OLEDs, the transport layer (CGL) plays a crucial role in performance, consisting 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 electrodes. The consumed electrons and holes in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively, after which the bipolar current gradually stabilizes. Typical CGL materials include n-type and p-type conductive dopants used in the transport layer.

[0148] In any of the compounds mentioned above used in each layer of an OLED device, hydrogen atoms may be partially or completely deuterated. The minimum amount of hydrogen in the deuterated compounds is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, any specifically mentioned substituents, such as but not limited to methyl, phenyl, and pyridyl, can have non-deuterated, partially deuterated, and fully deuterated versions. Similarly, classes of substituents, such as but not limited to alkyl, aryl, cycloalkyl, and heteroaryl, can also have non-deuterated, partially deuterated, and fully deuterated versions.

[0149] The various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. Accordingly, the claimed invention may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. The various theories of why the invention works are not intended to limit it.

[0150] Experiment Section

[0151] Synthesis of light-emitting body 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 mixture was cooled to room temperature (RT) and filtered by Celite. The residue was analyzed by column chromatography (10-20% ethyl acetate in heptane solution) to obtain 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 mixture was cooled and poured into ice water. A red solid was recovered by filtration (96% yield).

[0154] Synthesis of 9,9-dimethyl-9,10-dihydroacridine-4-amine [ka] 9,9-dimethyl-4-nitro-9,10-dihydroacridine (8.0 g, 31.4 mmol) and palladium carbon (2.0 g) were added to a flask containing ethyl acetate and stirred overnight. The reaction mixture was filtered and evaporated to obtain 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-dihydroacridine-4-amine (12.0 g, 53.5 mmol), triethoxymethane (7.93 g, 53.5 mmol), and p-toluenesulfonic acid (1.02 g, 5.35 mmol) were added to a flask equipped with a stirring bar and stirred overnight at 80°C. The reaction mixture was cooled to rt, diluted with ethyl acetate, and washed with aqueous sodium bicarbonate. The organic layers were combined, dried, evaporated, and the residue was purified by column chromatography (2% MeOH solution in DCM) to obtain an oily substance (89% yield).

[0157] Synthesis of 2-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-6,6-dimethyl-2,6-dihydroimidazo[4,5,1-de]acridine-11-iumtetrafluoroborate [ka] 6,6-dimethyl-6H-2l2,11l4-imidazo[5,4,3-de]acridine (156 mg, 0.666 mmol), (3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-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 stirring bar and cycled onto the line. Anhydrous DMF (6.658 mL) was added, and the reaction mixture was heated overnight to 120 °C. The reaction mixture was cooled to RT, and water was added to produce a white precipitate. The aqueous layer was extracted three times with ethyl acetate. The organic layers were combined, washed with saturated LiCl solution, dried over MgSO4, filtered, and degassed. The compound was isolated by column chromatography using a 1:1 CH3CN:DCM eluent. The pure fractions were combined and evaporated to obtain the desired compound as a white solid (55% yield).

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

[0159] Synthesis of light-emitting body 2 Synthesis of 5-iodo-1-phenyl-1H-imidazole [ka]

[0160] In a dry 1000 mL reaction tube, Cu(OTf)2 (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%) were added. Hexafluoroisopropanol (700 mL) was added, and the mixture was stirred at rt for 30 minutes, after which (1H-imidazole-5-yl)(phenyl)-13-iodanyl acetate (57.5 g, 173 mmol, 1.0 equiv) was added. The tube was capped, and the mixture was heated to 55 °C for 26 hours. The solvent was removed, and the product was isolated by column chromatography eluting with a hexane:siRNA mixture (100% hexane to 50% hexane / siRNA) to obtain the desired product (40% yield).

[0161] Synthesis of 2,2-dimethyl-1-(1-phenyl-1H-imidazole-5-yl)propan-1-one: [ka] 5-iodo-1-phenyl-1H-imidazole (0.320 g, 1.185 mmol, 1.0 equivalent) 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 equivalent) was added dropwise to the stirred solution over 2 minutes, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was cooled to -78°C, and pivaloyl chloride (0.290 mL, 2.37 mmol, 2.0 equivalent) was added dropwise over 2 minutes. The reaction mixture was stirred overnight at 23°C. The reaction mixture was quenched with saturated NH4Cl, diluted with siRNA, washed with saturated NaCl and DI water, and dried over Na2SO4. The crude product was purified by column chromatography (50% ethyl acetate:hexane) to obtain the desired product (42% yield).

[0162] Synthesis of 3,3-dimethyl-2-(1-phenyl-1H-imidazole-5-yl)butan-2-ol: [ka] 2,2-dimethyl-1-(1-phenyl-1H-imidazole-5-yl)propan-1-one (0.150 g, 0.657 mmol, 1 equivalent) and THF (3 mL) were added to a round-bottom flask. The mixture was cooled to -78°C for 15 minutes with stirring. Methyllithium (1.00 mL, 1.64 mmol, 2.5 equivalents) was added dropwise to the solution. The reaction mixture was stirred at -78°C for 1 hour, then warmed to room temperature for 4 hours. The reaction mixture was quenched with saturated NH4Cl at 0°C, diluted with ethyl acetate, and washed with saturated NaCl, saturated brine, and DI water. The reaction mixture was purified by column chromatography to obtain the desired product (65% ethyl acetate solution in hexane) (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-imidazole-5-yl)butan-2-ol (0.100 g, 0.409 mmol, 1 equivalent) and DCM (6 mL) were added to a flask equipped with a stirring bar. The mixture was stirred at 0°C for 30 minutes, after which aluminum trichloride (0.546 g, 4.09 mmol, 10 equivalents) was added all at once. The reaction mixture was stirred at 0°C for 1 hour, then heated to room temperature for 5 hours. The reaction mixture was cooled to 0°C, quenched with saturated Na2CO3, diluted with ethyl acetate, and washed with brine and DI water. The reaction mixture was purified by column chromatography (60% ethyl acetate in hexane solution) to obtain the desired product (96% yield).

[0165] Synthesis of 2-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-4,4,5,5-tetramethyl-4,5-dihydro-2H-10l4-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)pyridine-2-yl)-9H-carbazole-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 with a stirring bar. Anhydrous DMF (6.658 mL) was added, and the reaction mixture was heated overnight to 120 °C. The reaction mixture was cooled to RT, and the solvent was evaporated. The residue was dissolved in the minimum amount of DCM, Et2O was added, and the off-white solid was recovered by filtration (97% yield).

[0166] Synthesis of light-emitting body 2 [ka] 2-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-4,4,5,5-tetramethyl-4,5-dihydro-2H-imidazo[1,5-a]quinoline-10-iumtetrafluoroborate (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 stirring bar. 1,2-dichloroethane (3 mL) was added, and the reaction mixture was stirred overnight at RT. The reaction solvent was evaporated to obtain a foamy substance. 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 obtain a yellow solid (33% yield).

[0167] Synthesis of light-emitting body 3

[0168] Synthesis of 2-(2'-chloro-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka] In 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 heated to RT. It was then cooled again to -72°C. nBuLi was added and the reaction mixture was stirred for 1 hour. 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added and the solution was heated to RT and stirred overnight. The reaction mixture was diluted with diethyl ether and aqueous HCl solution, the aqueous phase was extracted, and the combined organic matter was dried over MgSO4 and filtered. The residue was purified by column chromatography to obtain 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] In a 2 L three-necked round-bottom flask, an aqueous solution of 2-(2'-chloro-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added, and the mixture was nitrogen bubbled 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 mixture was cooled to room temperature and diluted with ethyl acetate and brine. The aqueous phase was extracted with ethyl acetate. The combined organic matter was dried over MgSO4, filtered, and concentrated under vacuum to obtain a dark oily substance (63%).

[0170] Synthesis of 2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quarterphenyl]-2-amine: [ka] THF and K3PO4 were added to a 2 L three-necked round-bottom flask equipped with a partition and a stirring bar. Then, 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 SPhosPdG2 were added together. The reaction mixture was vigorously stirred at 60°C. After 24 hours, the reaction mixture was cooled to RT and ethyl acetate was added. The aqueous phase was extracted with ethyl acetate, the combined organic matter was dried over MgSO4, filtered, and vacuum concentrated to obtain a viscous black oily substance. This was dissolved in dichloromethane and packed into a large silica gel plug to obtain 2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quarterphenyl]-2-amine as a brown solid (83%).

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

[0172] Synthesis of 9H-tetrabenzo[b,d,f,h]azonine-8-amine [ka] A MeOH suspension of 8-nitro-9H-tetrabenzo[b,d,f,h]azonine was prepared in a 2 L round-bottom flask equipped with a septum and a stirring bar. Pd / C and hydrazine hydrate were added under nitrogen, and the mixture was vigorously stirred at 60°C to 65°C. After 3 hours, it was cooled and filtered through a Celite short pad. The filtrate was concentrated under vacuum to obtain a creamy suspension. This was diluted with water, and the aqueous phase was extracted with dichloromethane. The combined organic matter was washed with water and brine and dried over MgSO4. The residue was filtered and concentrated under vacuum to obtain 9H-tetrabenzo[b,d,f,h]azonine-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]azonine-8-amine (1 g, 2.99 mmol) was dissolved in triethoxymethane (24.90 ml, 150 mmol), sparged with argon for 5 minutes, and hydrogen chloride (0.295 ml, 3.59 mmol) (37% aqueous solution) was added all at once at room temperature. The reaction mixture was heated at 80°C for 16 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was diluted with ether and stirred for 30 minutes. The solid was filtered to obtain the product (0.9 g, 89%) as a white solid.

[0174] Synthesis of 1-(4-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-1-(tetrafluoro-15-boranyl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononona[1,2,3-cd]indene-2-id-1-ium-2-id [ka] 1,2a-Diazatribenzo[4,5:6,7:8,9]cyclononona[1,2,3-cd]indene (0.85 g, 2.468 mmol) and 9-(4-(tert-butyl)pyridine-2-yl)-2-(4-(mesityl(tetrafluoro-15-boranyl)-13-indanyl)phenoxy)-9H-carbazole (2.324 g, 3.21 mmol) were mixed 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 stirred at 110°C for 1 hour. The reaction mixture was cooled to RT, diluted with DCM, and evaporated until dry to obtain a brown oily substance. The substance was purified by column chromatography to obtain the product (2.05 g, 95%).

[0175] Synthesis of light-emitting body 3 [ka] 1-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-1-(tetrafluoro-15-boranyl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononona[1,2,3-cd]indene-2-id-1-ium-2-id (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. A concentrator was attached to the flask, and the reaction mixture was stirred under nitrogen at 125°C for 24 hours. The reaction mixture was cooled to RT, and the product was purified by column chromatography (0.1 g, 36%).

[0176] Synthesis of light-emitting element 4

[0177] 3-bromo-[1,1'-biphenyl]-2-amine: [ka] 300 ml of ethanol and 300 ml of water were added to a toluene (1.2 L) 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 a 2 L round-bottom flask. The flask was purged with nitrogen for 20 minutes, and the reaction mixture was stirred under reflux for 5 hours. The reaction mixture was cooled to RT, and 750 ml of water was added to separate it into two layers. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The residue was purified by column chromatography to obtain 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] In a 2 L round-bottom flask, 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)Cl2.CH2Cl2 (6.41 g, 7.79 mmol), and dimethyl sulfoxide (1 L) were introduced. The mixture was purged with nitrogen for 20 minutes, and then heated at 80°C for 3.5 hours. The reaction mixture was cooled to RT, and saturated ammonium chloride aqueous solution and ethyl acetate were added to the reaction mixture. The mixture was separated into two layers, the aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with 1 L of NaCl solution, dried over MgSO4, filtered, and vacuum concentrated. The oily substance was purified by column chromatography to obtain 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''''-kinkphenyl]-2'''-amine [ka] In a 2 L round-bottom flask, 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) were added, and the reaction mixture was stirred overnight under nitrogen at 60 °C. The reaction mixture was cooled to RT. Ethyl acetate was added, and the mixture separated into two layers. 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 obtain the product as a yellow solid. This solid was suspended in heptane and stirred for 3 hours. The suspension was filtered and washed with heptane to obtain 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] Potassium carbonate (18.25 g, 132 mmol) was added to a 2 L round-bottom flask containing a dimethyl sulfoxide (1000 ml) solution of 2-fluoro-3-nitro-[1,1':2',1'':2'',1''':3''',1''''-kinkphenyl]-2''''-amine (32 g, 66.0 mmol) and the flask was purged with nitrogen for 30 minutes. The reaction mixture was then stirred overnight at 155 °C. The reaction mixture was cooled to RT and cold saturated sodium chloride aqueous solution and ethyl acetate were added. The aqueous layer was extracted several times with ethyl acetate. The organic layers were combined, degassed to obtain an oily substance, and 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 obtain the product as an orange-yellow solid (37.15 g, 64%).

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

[0183] Synthesis of N-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azonine-8-amine [ka] Sodium tert-butoxide (0.489 g, 5.09 mmol), 10-phenyl-9H-tetrabenzo[b,d,f,h]azonine-8-amine (0.697 g, 1.697 mmol), and 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole (0.8 g, 1.697 mmol) were placed in a 250 mL round-bottom flask and flushed with N2. Then, toluene (6.79 ml) and Sphos-Pd-G2 (0.066 g, 0.085 mmol) were added, and the reaction mixture was stirred under reflux. The reaction mixture 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)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-3-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene-2a-ium bromide: [ka] N-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azonine-8-amine (45.9 g, 57.3 mmol) was dissolved in refluxed triethoxymethane (95 ml, 573 mmol) and cooled to RT. Hydrogen bromide (7.08 ml, 63.0 mmol) was added, and the mixture was stirred overnight at RT. The solvent was removed under vacuum, and the substance was purified by column chromatography to obtain the product as an off-white solid (34.22 g, 63.6% yield).

[0185] Synthesis of light-emitting element 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)pyridine-2-yl)-9H-carbazole-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)2 (6.92 g, 17.60 mmol) were dissolved / suspended in propionic acid (37 ml, 17.60 mmol). The reaction mixture was heated overnight at 150 °C. The reaction mixture was filtered, the filtered solid was redissolved in DCM, and separated with water. The organic layer was maintained and concentrated, and isolated by column chromatography to obtain a yellow solid (12.1 g, 67.6% yield).

[0186] Synthesis of light-emitting element 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. Then, ammonium acetate (2.61 g, 32.8 mmol) was added, followed by the addition of NBS (62.0 g, 345 mmol) in 10 portions of 6.2 g each, every 10 minutes. A saturated aqueous solution of Na2S2O3 (1.5 L) was added together with ethyl acetate, and the layers were separated. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The residue was purified by column chromatography to obtain the product as a red oil (72.5 g, 97%).

[0188] Synthesis of 4-bromo-2-(tert-butyl)-6-chloroaniline [ka] 4-bromo-2-(tert-butyl)aniline (63 g, 276 mmol) and DMF (1.05 L) were introduced into a 2 L round-bottom flask. The reaction mixture was purged with nitrogen for 20 minutes. Then, NCS (41.4 g, 304 mmol) was added all at once, 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 Na2S2O3 was added together with ethyl acetate, and the layers were separated. The organic layer was washed with water, dried over MgSO4, filtered, and concentrated under vacuum to obtain the product as a red oil (69.4 g, 94%).

[0189] Synthesis of 2-(tert-butyl)-6-chloroaniline [ka] 4-bromo-2-(tert-butyl)-6-chloroaniline (20 g, 76 mmol), palladium carbon (8.11 g, 7.62 mmol), and ethanol (160 mL) were introduced into a 350 mL pressure vessel. The reaction mixture was left under 10 psi of H2 for 4 hours. The mixture was filtered through a Celite pad and washed with ethanol. The filtrate was concentrated under vacuum. 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 MgSO4, filtered, and concentrated under vacuum to obtain 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] In a 2 L round-bottom flask, 2-(tert-butyl)-6-chloroaniline (25 g, 136 mmol) and 1,4-dioxane (550 ml) were added, followed by the addition of 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 then the reaction mixture was refluxed under nitrogen for 4 hours. After 4 hours, the mixture was filtered through a thin Celite pad, washed with ethyl acetate, and the filtrate was concentrated under vacuum. The product was purified by column chromatography to obtain an orange-yellow oily substance (26.2 g, 63%).

[0191] Synthesis of 3-(tert-butyl)-2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quarterphenyl]-2-amine [ka] In a 500 mL round-bottom flask, tetrahydrofuran (63 ml), freshly prepared tripotassium phosphate aqueous 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) were introduced, 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 mixture was then cooled to RT, ethyl acetate was added, and the layers were separated. The aqueous layer was further extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The product was purified by column chromatography to obtain a yellow solid (9.63 g, 78%).

[0192] Synthesis of 8-(tert-butyl)-10-nitro-9H-tetrabenzo[b,d,f,h]azonine [ka] A 1 L round-bottom flask containing a 385 ml solution of 3-(tert-butyl)-2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quarterphenyl]-2-amine (11 g, 23.75 mmol) in anhydrous dimethyl sulfoxide was mixed with 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 mixture was cooled to RT. Ice-cold saturated sodium chloride aqueous 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 under vacuum to obtain an oily substance, which was purified by column chromatography to obtain the product as an orange-yellow solid (4.79 g, 48%).

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

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

[0195] Synthesis of 3-(tert-butyl)-1-(3((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene-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)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonine-8-amine (3 g, 3.84 mmol) in triethyl orthoformate (32.0 ml, 192 mmol). The reaction mixture was heated at 100°C for 2 hours. Volatile substances were removed under reduced pressure, and the residue was ground with hexane to obtain the product as an off-white solid (2.7 g, 85%).

[0197] Synthesis of light-emitting element 5 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) were mixed in glacial acetic acid (48.3 ml) and sparged with nitrogen for 40 minutes. The reaction mixture was then refluxed overnight. The reaction mixture was diluted with a methanol / water mixture. The precipitate was collected by filtration, washed on a filter, and dried. The product was purified by column chromatography (1.1 g) to obtain a yellow solid.

[0198] Synthesis of light-emitting element 6 Synthesis of N-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonine-8-amine [ka] Sodium tert-butoxide (3.27 g, 34.0 mmol), 9H-tetrabenzo[b,d,f,h]azonine-8-amine (3.77 g, 11.27 mmol), and 2-(3-chlorophenoxy)-9-(4-(2,4,6-triisopropylphenyl)pyridine-2-yl)-9H-carbazole (6.5 g, 11.34 mmol) were added to a 250 mL round-bottom flask and flushed with nitrogen. The reaction mixture was heated to 80°C with toluene (90 ml). Then, SphosPdG3 (0.442 g, 0.567 mmol) was added and the reaction mixture was refluxed. After 2 hours, the reaction mixture was cooled, filtered by Celite, and purified by column chromatography to obtain a purple solid (8 g, 79%).

[0199] Synthesis of 1-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononona[1,2,3-cd]indene-2a-ium [ka] N-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonine-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, and a suspension was obtained after 2 hours. 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 obtain an off-white solid (2.5 g, 28.3%).

[0200] Synthesis of light-emitting element 6 [ka] A mixture of Pt(acac)2 (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)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononona[1,2,3-cd]indene (2.02 g, 2.1 mmol) in AcOH (20 mL) was spurged with nitrogen, and the reaction mixture was heated under reflux overnight. The reaction mixture was cooled to RT, and water was added to obtain a precipitate. The precipitate was purified by column chromatography to obtain a yellow solid (0.96 g, 46%).

[0201] Synthesis of light-emitting element 7 Synthesis of N-(3-((9-(4-(tert-butyl)pyridine-2-yl)-6-chloro-9H-carbazole-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azonine-8-amine [ka] A mixture of 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridine-2-yl)-6-chloro-9H-carbazole (2.59 g, 5.12 mmol), 10-phenyl-9H-tetrabenzo[b,d,f,h]azonine-8-amine (2.0 g, 4.87 mmol), and sodium 2-methylpropane-2-oleate (0.936 g, 9.74 mmol) was spurged with nitrogen, and then BINAP-PdG3 (0.242 g, 0.244 mmol) was added. The reaction mixture was heated overnight at 95°C. The reaction mixture was quenched with saturated ammonium chloride. The resulting slurry was filtered through a Celite plug and washed with dichloromethane. The filtrate was separated into water / 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 obtain an off-white solid (2.43 g, 59%).

[0202] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridine-2-yl)-6-chloro-9H-carbazole-2-yl)oxy)phenyl)-3-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene-2a-ium chloride [ka] Hydrochloric acid (0.388 ml, 4.65 mmol) was added to a mixture of N-(3-((9-(4-(tert-butyl)pyridine-2-yl)-6-chloro-9H-carbazole-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azonine-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, the residue was ground with heptane, and vacuum-dried to obtain an off-white solid (1.8 g, 70.2%). [ka] A mixture of 1-(3-((9-(4-(tert-butyl)pyridine-2-yl)-6-chloro-9H-carbazole-2-yl)oxy)phenyl)-3-phenyl-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene-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 mixture was then refluxed overnight. The reaction mixture was cooled to RT, and water was added to obtain a precipitate. The precipitate was filtered, the filter cake was washed with water, and dried by suction filtration. The solid was purified by column chromatography to obtain a yellow solid (1.2 g, 56.6%).

[0203] Synthesis of light-emitting element 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 mixture was heated overnight at 100°C. The reaction mixture was cooled to RT, and the solvent was removed by vacuum. The product was purified by column chromatography to obtain a yellow solid (0.44 g, 70.2%).

[0204] Synthesis of light-emitting element 8 [ka] In a 20 mL vial equipped with a stirring bar, 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) was added. The mixture was sparged with nitrogen and then heated overnight to 100°C. The reaction product was cooled to RT and filtered by Celite. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain a yellow solid (0.58 g, 88%).

[0205] Synthesis of light-emitting element 9 [ka] A 10:1 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) was added to a 20 mL vial with a stirring bar. The reaction mixture was sparged with nitrogen and heated overnight to 100 °C. The reaction mixture was cooled to RT and filtered by Celite. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain a yellow solid (0.61 g, 87%).

[0206] Synthesis of light-emitting body 10 Synthesis of 2'-bromo-2-fluoro-3-nitro-1,1'-biphenyl [ka] In a 1 L round-bottom flask, (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) were introduced. The reaction mixture was purged with nitrogen for 30 minutes with vigorous stirring, and then stirred overnight at 85°C. The reaction mixture was cooled to RT. After adding water, the two layers were separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The product was purified by column chromatography to obtain a white solid (86 g, 91%).

[0207] Synthesis of 2-chloro-2''-fluoro-3-methoxy-3''-nitro-1,1':2',1''-terphenyl [ka] In a 2 L round-bottom flask, 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) were introduced. The reaction mixture was purged with nitrogen for 30 minutes, and then stirred under nitrogen at 60°C for 5 hours. The reaction mixture was cooled to RT. After adding water (1 L), the mixture was separated into two layers. The aqueous layer was extracted with ethyl acetate (3 × 300 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The crude product was purified by column chromatography to obtain a white solid (80.3 g, 95%).

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

[0209] Synthesis of 4-methoxy-10-nitro-9H-tetrabenzo[b,d,f,h]azonine [ka] A 2 L round-bottom flask containing a 1 L dry DMSO (1 L) solution of 2'''-fluoro-6'-methoxy-3'''-nitro-[1,1':2',1'':2'',1'''-quarterphenyl]-2-amine (28 g, 61.8 mmol) was mixed with 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 hours. The reaction mixture was cooled to room temperature. After adding 4 L of ice-cold saturated NaCl solution, 750 mL of ethyl acetate was added, and the mixture was separated into two layers. The aqueous layer was extracted with ethyl acetate (4 × 500 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum at 45 °C to obtain a viscous, maroon oily substance. The crude substance was purified by column chromatography to obtain an orange-yellow solid (51.4 g, 85%).

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

[0211] Synthesis of 10-nitro-9H-tetrabenzo[b,d,f,h]azonine-4-yltrifluoromethanesulfonate [ka] 10-nitro-9H-tetrabenzo[b,d,f,h]azonine-4-ol (25 g, 63.7 mmol) and dried dichloromethane (600 mL) were introduced into a 2 L round-bottom flask. 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 bath. Next, trifluoromethanesulfonic anhydride (11.26 ml, 66.9 mmol) was added dropwise over 50 minutes. The reaction mixture was slowly heated to RT and stirred at room temperature for 16 hours. A saturated aqueous solution of sodium bicarbonate (1 L) was added, and the mixture was separated into two layers. The aqueous layer was extracted with dichloromethane (3 × 300 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The crude substance was purified by column chromatography to obtain an orange solid (50.7 g, 97%).

[0212] Synthesis of 10-nitro-4-phenyl-9H-tetrabenzo[b,d,f,h]azonine [ka] In a 1 L round-bottom flask, 10-nitro-9H-tetrabenzo[b,d,f,h]azonine-4-yltrifluoromethanesulfonate (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) were introduced. 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 RT. After adding water (500 mL), the mixture was separated into two layers. The aqueous layer was extracted with ethyl acetate (3 × 250 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The crude product was purified by column chromatography to obtain a red solid (16.8 g, 96%).

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

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

[0215] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-7-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene-2a-ium [ka] Hydrochloric acid (0.531 ml, 6.37 mmol) was added to a mixture of N-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-13-phenyl-9H-tetrabenzo[b,d,f,h]azonine-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, the residue was ground with heptane, and vacuum-dried to obtain an off-white solid (3.0 g, 83%).

[0216] Synthesis of light-emitting body 10 [ka] A mixture of 1-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-6-phenyl-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene-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 mixture was then refluxed overnight. The reaction mixture 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 obtain a yellow solid (2.6 g, 87%).

[0217] Synthesis of light-emitting element 11 Synthesis of 2-fluoro-3''-methoxy-3-nitro-[1,1':2',1'':2'',1''':3''',1''''-kinkphenyl]-2''''-amine: [ka] Potassium phosphate (480 ml, 240 mmol) was added under nitrogen to a suspension of dioxane (240 ml) containing 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). The reaction mixture was heated to 90°C for 3 hours. 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 under vacuum, and the residue was purified by column chromatography to obtain 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''''-kinkphenyl]-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 hours. After cooling, the reaction was quenched with water (300 mL) and then extracted with ethyl acetate (300 mL). The organic layer was recovered, and the aqueous layer was extracted with ethyl acetate (300 mL). The organic layers were concentrated together, and the residue was purified by column chromatography to obtain the desired product as an orange solid (8.76 g, 68%).

[0219] Synthesis of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonine-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 hours. After cooling, water (200 mL) and ethyl acetate (200 mL) were added while stirring. The organic layer was collected and the solvent was removed. The residue was purified by column chromatography to obtain an orange powder (6.5 g, 67%).

[0220] Synthesis of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonine-4-yltrifluoromethanesulfonate [ka] Trifluoromethanesulfonic acid anhydride (8.65 g, 30.7 mmol) was added at 0°C to a suspension of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azonine-4-ol (7 g, 15.33 mmol) and triethylamine (4.66 g, 46.0 mmol) in CH2Cl2 (200 ml). The reaction mixture was then diluted with CH2Cl2 (100 mL) and washed with water (100 mL x 2). The solvent was then removed, and the residue was purified by column chromatography to obtain 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]azonine-4-yltrifluoromethanesulfonate (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), an aqueous solution of potassium phosphate (122 ml, 61.2 mmol) was added under nitrogen. The reaction mixture was heated to 80°C for 3 hours. 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 obtain 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 (2g, 3.87 mmol), hydrazine hydrate (3.88g, 77 mmol), and palladium (0.412g, 0.387 mmol) carbon in EtOH (200 ml) / CH2Cl2 (20 mL) was heated to 90°C for 3 hours. After cooling, the reaction mixture was filtered through Celite and washed with ethyl acetate. All solvent was removed, and the residue was purified by column chromatography to obtain the desired product (1.2 g, 63%).

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

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

[0225] Synthesis of light-emitting element 11 [ka] A mixture of potassium tetrachloroplatinate (2.52 g, 6.07 mmol), 1-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-3,7-diphenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclonona[1,2,3-cd]indene-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 mixture 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 substance was concentrated, and the product was purified by column chromatography to obtain a yellow solid (1.2 g, 18.11%).

[0226] Synthesis of light-emitting element 12 Synthesis of 2-chloro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline [ka] 2-Bromo-6-chloroaniline (8.2g, 39.7mmol), bis(pinacorato)diborone (30.3g, 119mmol), and KOAc (15.59g, 159mmol) are suspended in DMSO (80mL) and then dissolved in Pd(dppf)Cl2 under nitrogen. * CH2Cl2 (1.622 g, 2 mmol) was added. The reaction mixture was then heated under nitrogen to 90°C for 20 hours. After cooling, ethyl acetate (200 mL) and aqueous HCl solution (0.5 M, 100 mL) were added while 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 x 2). The organic solution was then dried over Na2SO4. After solvent removal, the residue was purified by column chromatography to obtain 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), n-BuLi (23 mL, 2.5 M, 27.5 mmol) was added dropwise under nitrogen at -78 °C. After 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 slowly added at -78 °C. After addition, the reaction temperature was gradually reduced to room temperature and stirred for a further 2 hours. Water (200 mL) and ethyl acetate (200 mL) were added while stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (200 mL). The solvent was removed from the combined organic layers, and the residue was purified by column chromatography to obtain the desired product (11 g, 64%).

[0228] Synthesis of 2''-bromo-2-fluoro-3-nitro-1,1':2',1''-terphenyl [ka] To a dioxane (140 mL) suspension of 1-bromo-2-fluoro-3-nitrobenzene (10.04 g, 45.6 mmol), boronate 268-4 (12.6 g, 35.1 mmol), and K2CO3 aqueous solution (70.2 mL, 2 M, 140.4 mmol), Pd(Ph3P)4 (2.028 g, 1.755 mmol) was added under N2. The reaction mixture was heated overnight under nitrogen to 85 °C. 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 was removed from the combined organic layers, and the residue was purified by column chromatography (9 g, 68%).

[0229] 3-Chloro-2'''-fluoro-3'''-nitro-[1,1':2',1'':2'',1'''-quarterphenyl]-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), an aqueous solution of K3PO4 (103 mL, 0.5 M, 51.6 mmol) was added under N2 conditions. The reaction mixture was heated to 60 °C for 3 hours. 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 was removed from the combined organic layers. The residue was purified by column chromatography to obtain 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'''-quarterphenyl]-2-amine (7.5 g, 17.9 mmol). The reaction mixture was heated to 150°C (oil bath temperature) for 3 hours. After cooling, the reaction product was quenched with water (100 mL) and then extracted with ethyl acetate (100 mL x 2). The combined organic solution was washed with brine (100 mL x 2). The solvent was then removed under vacuum, and the residue was purified by column chromatography to obtain 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 conditions, 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 hours. 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 was removed from the combined organic layers, and the residue was purified by column chromatography to obtain a solid product (8.92 g, 100%).

[0232] Synthesis of 10-([1,1':3',1''-terphenyl]-5'-yl)-9H-tetrabenzo[b,d,f,h]azonine-8-amine [ka] Pd / C (1 g, 10%, 0.945 mmol) was added to a mixed solvent system 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 ethanol (100 mL) and CH2Cl2 (20 mL). The reaction mixture was heated under reflux for 3 hours. After cooling, the reaction mixture was filtered through Celite and washed with CH2Cl2 (20 mL x 5). The solvent was removed, and the residue was purified by column chromatography to obtain an off-white solid product (1.35 g, 50%).

[0233] Synthesis of 10-([1,1':3',1''-terphenyl]-5'-yl)-N-(3-((9-(4-(tert-butyl)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonine-8-amine: [ka] A mixture of 10-([1,1':3',1''-terphenyl]-5'-yl)-9H-tetrabenzo[b,d,f,h]azonine-8-amine (1.5 g, 2.67 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridine-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. Then, sodium 2-methylpropane-2-oleate (0.512 g, 5.33 mmol) was added, and sparging was continued for 10 minutes. The reaction mixture was then refluxed for 20 hours. The reaction mixture was quenched with saturated ammonium chloride (20 mL) and diluted with ethyl acetate (20 mL). The resulting slurry was filtered through a Celite plug (0.5''). The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (2 × 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 obtain 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)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononona[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)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azonine-8-amine (2.32 g, 2.434 mmol) in triethyl orthoformate (20.26 ml, 122 mmol). The reaction mixture was heated to 100°C for 16 hours. Volatile substances were removed under reduced pressure, and the residue was pulverized over warm hexane (2 × 25 mL) to obtain an off-white solid (2.35 g, 85% yield).

[0235] Synthesis of light-emitting element 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)pyridine-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononona[1,2,3-cd]indene-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 mixture was refluxed overnight at 120°C. The reaction mixture was diluted with water, and the aqueous layer was extracted several times with DCM. The organic layers were combined, dried, concentrated, and the residue was purified by column chromatography to obtain a yellow solid (1.6 g, 73%).

[0236] Device Data

[0237] Eight types of OLED devices were fabricated to compare the performance of several examples of the present invention's compounds with comparative compounds used in OLED applications. OLED1 to OLED7 contained light-emitting compounds 2, 3, 6, 4, 5, and 7, which are examples of the present invention's compounds, respectively, while OLED8 contained a comparative compound as the light-emitting compound. Device performance data is shown in Table 1 below.

[0238] An OLED was grown on a glass substrate pre-coated with an indium tin oxide (ITO) layer having a sheet resistance of 15 Ω / sq. Prior to the deposition or coating of the organic layer, the substrate was degreased with a solvent, and then subjected to oxygen plasma treatment at 50 W, 100 mTorr for 1.5 minutes, followed by UV ozone treatment for 5 minutes.

[0239] OLEDs are produced under high vacuum (<10 -6 The devices were fabricated by thermal deposition in Torr. The anode electrode was 750 Å indium tin oxide (ITO). The device examples had, in order from the ITO surface, 100 Å compound 1 (HIL), 250 Å compound 2 (HTL), 50 Å compound 3 (EBL), 300 Å compound 3 (50% compound 4 and 12% luminescent material doped) (EML), 50 Å compound 4 (BL), 300 Å compound 5 (35% compound 6 doped) (ETL), 10 Å compound 5 (EIL), and a 1,000 Å Al (cathode) organic layer. Immediately after fabrication, all devices were sealed in a nitrogen glove box (<1 ppm H2O and O2) with a moisture getter packaged in a glass lid sealed with epoxy resin. Doping percentages are deposition percentages. Table 1: Summary of OLED performance [Table 1] TIFF2026065028000188.tif240170 TIFF2026065028000189.tif49170

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

[0241] This application discloses a platinum N-heterocyclic carbene (NHC) complex characterized by a carbene-N substituent bonded to 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 compared to comparative compounds where the carbene-N phenyl substituent is not strapped to the carbene. In most cases, the spectral shape is much narrower in the case of the strapped NHC than in the comparative compounds, improving color purity. Generally, the FWHM of the emission spectrum of phosphorescent complexes is broad, typically exceeding 50 nm, as shown in the comparative example here. Achieving a narrow FWHM has been a long-desired goal. A narrower FWHM leads to better color purity in display applications. In past OLED research, narrowing the linear shape has been achieved gradually on a nanometer scale. As seen here, the present invention's compounds with strapping can significantly reduce the FWHM number to less than 40 nm, or even 30 nm. The compounds of the present invention also shift towards the more desirable blue side, allowing the devices to be more efficient with purer colors. Another notable improvement is that the strapping compounds improve device efficiency by approximately twofold in almost all examples. Such improvements are considered very significant and represent an important step toward the commercialization of these present invention light emitters. The remarkable performance improvements seen in the above data were unexpected, given that the examples of the compounds of the present invention (light emitter 2, light emitter 3, light emitter 4, light emitter 5, light emitter 6, light emitter 7, light emitter 13) have a similar structure to the comparative compounds, except that they differ only in the additional strap portion.

Claims

1. The following ligand L Ａ A material for use in organic light-emitting devices (OLEDs), characterized by containing the following: 【Chemistry 1】 (In the formula, ring A is independently a 5-membered to 10-membered heteroring; X １ ~X ６ Each of these is independently either C or N; K ３ is a direct bond, O, or S; R Ａ , R Ｂ , and R Ｃ Each independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R １ 、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; The ligand L Ａ It forms a complex with metal M via the two dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; The ligand L Ａ It can combine with other ligands to form tridentate, quadrdentate, quindentate, or hexadentate ligands; Any two adjacent R Ａ , R Ｂ , R Ｃ , or R １ The aforementioned materials are as follows: 【Chemistry 2】 They can bond or condense to form a ring, provided they do not contain either of the structures shown; At least one of the following conditions (1) to (5) is true: (1) X １ ~X ３ However, each of them is C. (2) Two adjacent R Ａ The substituents attach to form a fused ring with respect to ring A. (3) Ring A is a 7-membered to 10-membered heteroring. (4) Ligand L Ａ Equation II is (5) M is not Pt.

2. R １ , R Ａ , and R Ｂ The material according to claim 1, wherein each substituent is independently 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, sulfanil, and combinations thereof.

3. X １ ~X ３ However, each is either C or X. ４ ~X ６ However, each is either C or X. １ ~X ６ However, each of these is the material according to claim 1, which is C.

4. Two adjacent R Ａ The material according to claim 1, wherein a substituent is bonded to form a fused ring with respect to ring A.

5. When ring A is a 7-membered ring, an 8-membered ring, a 9-membered ring, or a 10-membered ring, four adjacent R Ａ The material according to claim 1, wherein substituents are bonded to form two fused rings relative to ring A.

6. When ring A is an 8-membered ring, a 9-membered ring, or a 10-membered ring, there are a total of six adjacent R Ａ The material according to claim 1, wherein substituents bond to each other to form three separate rings, all of which condense with ring A.

7. The material according to claim 1, having the following structure. 【Transformation 3】 (In the formula, M １ is either Pd or Pt; Parts C and D are independently monocyclic or polycyclic structures containing five-membered and / or six-membered carbon rings or heterocyclic structures; Z １ and Z ２ Each of these is independently either C or N; K １ _K ２ , and K ３ Each is independently selected from the group consisting of direct bonds, O, and S, and K １ _K ２ , or K ３ At least two of them are direct connections; L １ , L ２ , and L ３ These are, independently, directly bonded: BR, BRR, NR, PR, O, S, Se, C=O, S=O, SO ２ Selected from the group consisting of CRR', SiRR', GeRR', alkyl, cycloalkyl, and combinations thereof, L １ and L ２ At least one of the following exists; n1, n2, and n3 are either 0 or 1, and n1 + n2 + n3 = 2 or 3; X ７ ~X ９ Each of these is independently either C or N; R Ｃ and R Ｄ Each independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R Ｃ and R Ｄ Each of these substituents is independently 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; Any two adjacent R Ａ , R Ｂ , R Ｃ , R Ｄ , or R １ These elements can bond or condense with each other to form chemically possible rings.

8. The material according to claim 7, wherein both portion C and portion D are six-membered aromatic rings, or portion C is a five-membered or six-membered heteroring.

9. L １ The material according to claim 7, wherein the material is O, SiRR', or CRR'.

10. L ２ The material according to claim 7, wherein the bond is direct or NR.

11. The material according to claim 7, having the following structure. 【Chemistry 4】 (In the formula, Z ３ is C or N; Any two adjacent R Ａ , R Ｂ , R Ｃ , R Ｄ , or R １ They combine or condense with each other to form a ring.

12. The material according to claim 11, selected from the group consisting of the following. 【Transformation 5】 【change】 【change】 (In the formula, R ｘ and R ｙ Each is selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; R Ｇ Each of these substituents is independently 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.

13. The material according to claim 7, having the following structure. 【Transformation 6】 (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’ Selected from the group consisting of 9-(Rs)(Rt)(Ru), where s, t, and u are each independent integers from 1 to 87, 【Transformation 7】 where 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 s 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), selected from the group consisting of, where s, t, and u are each independently integers from 1 to 87, where 【Transformation 8】 【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 You can choose from the group consisting of 33-(Rs)(Rt)(Ru), where s, t, and u are each independent integers from 1 to 87, and in the formula, 【Chemistry 9】 【change】 【change】 In the formula, R1 to R87 have the following structure. 【Chemistry 10】 【change】 【change】

14. The material according to claim 7, selected from the group consisting of the following. 【Chemistry 11】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】

15. The aforementioned material 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 The material according to claim 1, having a formula selected from the group consisting of ). (In the formula, L Ｂ and L Ｃ These are each bidentate ligands; L Ａ , L Ｂ , and L Ｃ They are different from each other; At least one of the following (a) to (d) is true: (a) Ring A is a 7-membered to 10-membered heteroring. (b) Ligand L Ａ Equation II is (c) Two adjacent R Ａ The substituents attach to form a fused ring with respect to ring A. (d) The material is 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 It has an expression selected from the group consisting of the following:

16. The following ligand L Ａ A material for use in organic light-emitting devices (OLEDs), characterized by containing the following: 【Chemistry 12】 (In the formula, ring A is independently a 5-membered to 10-membered heteroring; X １ ~X ６ Each of these is independently either C or N; K ３ is a direct bond, O, or S; R Ａ , R Ｂ , and R Ｃ Each independently represents zero, mono, or the maximum number of possible permutations on the associated ring; R １ , R Ａ , R Ｂ , R Ｃ Each of these substituents is independently selected from the group consisting of hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, gelmyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphine, and combinations thereof; The ligand L Ａ It forms a complex with metal M via the two dashed lines; M is Ir and can coordinate to other ligands; The ligand L Ａ It can combine with other ligands to form tridentate, quadrdentate, quindentate, or hexadentate ligands; Any two adjacent R Ａ , R Ｂ , R Ｃ , or R １ They can bond or condense to form a ring; At least one of the following (a) to (d) is true: (a) Ring A is a 7-membered to 10-membered heteroring. (b) Ligand L Ａ Equation II is (c) Two adjacent R Ａ The substituents attach to form a fused ring with respect to ring A. (d) The material is 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 The formula is selected from the group consisting of ), where L Ｂ and L Ｃ These are each bidentate ligands, and L Ａ , L Ｂ , and L Ｃ They are all different from each other.

17. Organic light-emitting devices (OLEDs), A-scatter, Cathode and, It includes an organic layer disposed between the anode and the cathode, An organic light-emitting device (OLED) characterized in that the organic layer comprises the material described in claim 1 or 16.

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