Blue and narrow-band green and red light-emitting metal complexes, and organic light-emitting diodes and light-emitting devices comprising the same

Abstract

This application relates to blue and narrow-band green and red emitting metal complexes, and organic light emitting diodes and light emitting devices comprising the same. The invention includes tetradentate platinum(II) complexes for narrow-band green and red phosphorescent emitters. The invention also includes blue-emitting metal complexes with a six-membered chelate ring based on a fused carbazole. The invention also includes organic light emitting diodes (OLEDs) containing these complexes, and devices containing these OLEDs.

Description

This application is a divisional application of the invention patent application filed on March 8, 2019, with application number 201910177248.8 and entitled "Blue light and narrow-band green light and red light emitting metal complexes, and organic light-emitting diodes and light-emitting devices comprising the same". Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Patent Application Nos. 62 / 640,656 (filed March 9, 2018) and 62 / 640,659 (filed March 9, 2018), both of which are incorporated herein by reference in their entirety. Technical Field

[0002] This invention relates to blue-emitting metal complexes having a six-membered chelate ring based on fused carbazole, organic light-emitting diodes (OLEDs) comprising these complexes, and devices comprising these OLEDs. The invention also relates to tetradentate platinum(II) complexes for narrowband green and red phosphorescent emitters, organic light-emitting diodes (OLEDs) comprising these complexes, and devices comprising these OLEDs. Background Technology

[0003] Phosphorescent ring metallized complexes have attracted attention due to their potential application as phosphorescent emitters in organic light-emitting diodes (OLEDs). Through tireless material design, high-efficiency OLEDs spanning various parts of the visible spectrum have been achieved. However, developing stable and efficient blue light emitters, as well as stable narrowband green and red light emitters, remains a challenge. Summary of the Invention

[0004] A series of platinum(II) complexes have been designed and synthesized. These complexes offer improved color purity and enhanced operational stability and are suitable for use in luminescent marking, OLED emitters, and lighting applications. Attached Figure Description

[0005] Figure 1A A schematic diagram of the energy levels of a luminescent complex with a carbazole framework is depicted. Figure 1B A schematic diagram of the energy levels of a luminescent complex with a fused aryl group in the carbazole skeleton is depicted.

[0006] Figure 2 Organic light-emitting diodes (OLEDs) are depicted.

[0007] Figure 3 The emission spectrum of the platinum(II) complex synthesized according to Example 2 is shown. Detailed Implementation

[0008] General formulas I to VIII represent blue-emitting platinum complexes suitable for full-color displays and lighting applications, which have a six-membered chelate ring based on fused carbazole. The emission spectral bandwidth of general formulas I to VIII complexes decreases at room temperature, which is at least partly attributed to the introduction of fused aryl groups into the carbazole skeleton. As depicted, general formulas I to VIII complexes have a symmetry axis through M and X, i.e., between each pair of Ar... n The axis of symmetry between n and n is an integer from 1 to 4.

[0009]

[0010] General Formula I

[0011]

[0012] Formula II

[0013]

[0014] Formula III

[0015]

[0016] Formula IV

[0017]

[0018] General formula V

[0019]

[0020] General formula VI

[0021]

[0022] General Formula VII

[0023]

[0024] General Formula VIII

[0025] In general formulas I to VIII:

[0026] M is Pt 2+ ;

[0027] R 1 R 2 R 3 and R 4 If present, each of them independently represents hydrogen, deuterium, trideuterium methyl, pentadeuterium phenyl, halogen, hydroxyl, nitro, nitrile, thiol; or substituted or unsubstituted amino, alkoxy, aryl or C1-C4 alkyl.

[0028] Each n independently represents the allowed integer valence;

[0029] Y 1a Y 1b Y 1c Y 1d Y 1e Y 1f Y 2a Y 2b Y 2c Y 2d Y 2e Y 2f Y 3a Y 3b Y 3c Y 3d Y 3e Y 3f Y 4a Y 4b Y 4c Y 4d Y 4e and Y 4f Each can independently represent C, N, Si, O, or S; and

[0030] X, X 1 and X 2 Each of the elements exists or does not exist, and each X, X' exists. 1 and X 2 Independently representing a single bond, NR, PR, CRR', SiRR', O, S, S=O, O=S=O, Se, Se=O or O=Se=O, wherein R and R' each independently represent hydrogen, deuterium, trideuterium methyl, pentadeuterium phenyl, nitrile, halogen, hydroxyl, nitro, thiol, or substituted or unsubstituted alkoxy, aryl, amino or C1-C4 alkyl.

[0031] Ar 1 Ar 2 Ar 3 and Ar 4 Independently represents six-membered aryl and heteroaryl rings, including phenyl and pyridyl rings.

[0032] Figure 1A Energy level diagrams of luminescent complexes with a carbazole framework (such as PtNON described below) were depicted.

[0033]

[0034] These complexes exhibit extremely broad room-temperature emission spectra. Figure 1B Energy level diagrams of luminescent complexes of general formulas I to VIII with fused aryl groups in the carbazole skeleton are depicted. An example of PtNON-S56 is described below.

[0035]

[0036] The fusion of aryl groups with the carbazole skeleton of complexes of general formulas I to VIII expands the conjugated system, thereby promoting energy level shifts. Figure 1A Compared to the energy level diagram in the middle, Figure 1B The energy level diagram in the middle shows 3 The energy of the LC (ligand-centered) state decreases, while 3 Even if the MLCT (metal-to-ligand charge transfer) state energy decreases, it only decreases slightly and remains essentially the same. Therefore, at room temperature, 3 LC state and 3 The increased band gap between MLCT states is at least partly attributed to the expanded conjugated system. It is believed that this shift leads to a greater band gap in the T1 state compared to complexes with a carbazole skeleton but without fused aryl groups. 3 The enhanced LC characteristics result in a narrower room-temperature emission spectrum.

[0037] Examples of compounds of general formulas I to VIII are provided below, where each R 1 and R 2 As defined above.

[0038]

[0039]

[0040]

[0041]

[0042] General formula IX represents a tetradentate platinum(II) complex of narrow green and red phosphorescent emitters suitable for full-color displays and lighting applications.

[0043]

[0044] General formula IX

[0045] In general formula IX:

[0046] Ar 1 Ar 2 Ar 3 and Ar 4 Each individually represents an aryl, heteroaryl, fused aryl, or fused heteroaryl group having 5 to 10 ring atoms;

[0047] R 1 R 2 R 3 and R 4Each can independently represent hydrogen, deuterium, trideuterium methyl, pentadeuterium phenyl, halogen, hydroxyl, nitro, nitrile, thiol; or substituted or unsubstituted alkoxy, aryl, amino, or C1-C4 alkyl.

[0048] Each n independently represents the allowed integer valence;

[0049] Y 1a Y 1b Y 1c Y 2a Y 2b Y 2c Y 2d Y 3a Y 3b Y 3c Y 3d Y 4a Y 4b and Y 4c Each can independently represent C, N, Si, O, or S;

[0050] X represents O, S, NR, CRR', SiRR', PR, BR, S=O, O=S=O, Se, Se=O or O=Se=O, wherein each R and R' independently represents hydrogen, deuterium, trideuterium methyl, pentadeuterium phenyl, hydroxyl, nitro, nitrile, thiol, or substituted or unsubstituted alkoxy, aryl, amino or C1-C4 alkyl;

[0051] L 1 and L 2 Each may or may not exist independently, and if present, each independently represents an alkyl, alkoxy, alkenyl, alkynyl, hydroxyl, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, or heterocyclic linking group.

[0052] Applicable to Ar 1 Ar 2 Ar 3 and Ar 4 Examples of aryl, heteroaryl, fused aryl, or fused heteroaryl rings having 5 to 10 ring atoms include phenyl, pyridyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, naphthyl, benzimidazolyl, quinazolinyl, and quinolinyl.

[0053] Examples of complexes of general formula IX are shown below, wherein:

[0054] Every Z that exists 1 Z 2 Z 3 and Z 4 Independently represent C or N; and

[0055] Every existing R 5 and R 6Independently representing hydrogen, deuterium, trideuterium methyl, pentadeuterium phenyl, halogen, hydroxyl, nitro, nitrile, thiol; or substituted or unsubstituted alkoxy, aryl, amino, or C1-C4 alkyl; and

[0056] Each n independently represents an allowed integer valence.

[0057]

[0058]

[0059]

[0060]

[0061] Examples of complexes of general formula IX are shown below, wherein each R and R', if present, independently represents a substituted or unsubstituted alkoxy, aryl, heteroaryl, trideuteryl, pentadeuterylphenyl, or C1-C4 alkyl.

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109] .

[0110] As mentioned in this article, a linking atom or group connects two atoms, such as an N atom and a C atom. In one aspect of this article, the linking atom or group is referred to as L. 1 L 2 L 3 As disclosed herein. If the valence allows, the linking atom may optionally be connected to other chemical moieties. For example, in one aspect, once oxygen is bonded to two groups (e.g., N and / or C groups), no other chemical groups are connected because the valence is satisfied. In another aspect, when carbon is the linking atom, two additional chemical moieties may be connected to said carbon. Suitable chemical moieties include amines, amides, thiols, aryl, heteroaryl, cycloalkyl, and heterocyclic moieties. The term "cyclic structure" or similar terms used herein refer to any cyclic chemical structure, including (but not limited to) aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic, carbene, and... N- Heterocyclic carbene.

[0111] As used herein, the term “substitution” is intended to include all permissible substituents of an organic compound. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched carbocyclic and heterocyclic, as well as aromatic and non-aromatic substituents of an organic compound. Illustrative substituents include those described below, for example. For a suitable organic compound, permissible substituents may be one or more and may be the same or different. For the purposes of this disclosure, heteroatoms (e.g., nitrogen) may have hydrogen substituents and / or any permissible substituents of the organic compound described herein that satisfy the heteroatom valence. This disclosure is not intended to be limited in any way to permissible substituents of an organic compound. Furthermore, the implied condition included by the terms “substitution” or “replaced by” is that such substitution conforms to the permissible valence of the substituted atom and the substituent, and that the substitution produces a stable compound, such as a compound that does not spontaneously undergo transformations (e.g., rearrangement, cyclization, elimination, etc.). It is also contemplated in some aspects that, unless the contrary is explicitly stated, individual substituents may be further optionally substituted (i.e., further substituted or unsubstituted).

[0112] When defining various terms, "A" 1 “A” 2 “A” 3 “A” 4 "and "A 5 "These symbols are used as general symbols in this document to denote various specific substituents. These symbols can be any substituents, not limited to those disclosed herein, and while they are defined as certain substituents in one example, they can be defined as some other substituents in another example."

[0113] As used herein, the term "alkyl" is a branched or unbranched saturated hydrocarbon group with 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetradecyl, etc. Alkyl groups can be cyclic or acyclic. Alkyl groups can be branched or unbranched. Alkyl groups can also be substituted or unsubstituted. For example, an alkyl group can be substituted by one or more groups (including (but not limited to) alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfonic acid-oxo, or thiol), as described herein. A "low carbon number alkyl" group is an alkyl group containing one to six (e.g., one to four) carbon atoms.

[0114] Throughout this specification, "alkyl" is generally used to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituents on the alkyl group. For example, the terms "halogenated alkyl" or "halogenated alkyl" specifically refer to an alkyl group substituted with one or more halogen groups (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino and similar groups as described below. When "alkyl" is used in one example and a specific term such as "alkyl alcohol" is used in another example, it is not intended to imply that the term "alkyl" is used without mentioning the specific term, such as "alkyl alcohol" and similar terms.

[0115] This practice also applies to other groups described herein. That is, while terms such as “cycloalkyl” refer to both unsubstituted and substituted cycloalkyl moieties, substituted moieties may be specifically identified otherwise herein; for example, a specifically substituted cycloalkyl group may be referred to as, for example, “alkylcycloalkyl.” Similarly, a substituted alkoxy group may be specifically referred to as, for example, “haloalkoxy,” and a specifically substituted alkenyl group may be, for example, “alkenyl alcohol,” etc. Furthermore, the practice of using both general terms (e.g., “cycloalkyl”) and specific terms (e.g., “alkylcycloalkyl”) is not intended to imply that the general terms do not include the specific terms.

[0116] As used herein, the term "cycloalkyl" refers to a carbon-based non-aromatic ring consisting of at least three carbon atoms. Examples of cycloalkyl include (but are not limited to) cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornel, etc. The term "heterocyclic alkyl" is a type of cycloalkyl as defined above and is included within the meaning of the term "cycloalkyl," wherein at least one carbon atom in the ring is replaced by a heteroatom (e.g., (but not limited to) nitrogen, oxygen, sulfur, or phosphorus). Cycloalkyl and heterocyclic alkyl groups can be substituted or unsubstituted. Cycloalkyl and heterocyclic alkyl groups can be substituted with one or more groups, including (but not limited to) alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfonic acid-oxo, or thiol groups as described herein.

[0117] As used herein, the terms "alkoxy" and "alkoxyl" refer to alkyl or cycloalkyl groups bonded by ether bonds; that is, "alkoxy" can be defined as -OA. 1 A 1 These are alkyl or cycloalkyl groups as defined above. "Alkoxy" also includes polymers of alkoxy groups just described; that is, alkoxy groups can be polyethers, such as -OA. 1 -OA 2 or -OA 1 -(OA 2 ) a -OA 3 Where "a" is an integer from 1 to 200 and A 1 A 2 and A 3 It is an alkyl and / or cycloalkyl group.

[0118] As used herein, the term "alkenyl" refers to a hydrocarbon group with 2 to 24 carbon atoms whose structural formula contains at least one carbon-carbon double bond. Asymmetric structures, such as (A... 1 A 2 C=C(A) 3 A 4 ), hoping to include E and Z Isomers. This can be deduced from the structural formulas of the asymmetric alkenes described herein, or it can be explicitly indicated by the bond symbol C=C. The alkenyl group may be substituted with one or more groups, including (but not limited to) alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogroup, hydroxyl, ketone, azide, nitro, silyl, sulfonic acid-oxo, or thiol.

[0119] As used herein, the term "cycloalkenyl" is a carbon-based non-aromatic ring consisting of at least three carbon atoms and containing at least one carbon-carbon double bond (i.e., C=C). Examples of cycloalkenyl groups include (but are not limited to) cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornyl, etc. The term "heterocyclic alkenyl" is a type of cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkenyl," wherein at least one carbon atom in the ring is substituted by a heteroatom (e.g., (but not limited to) nitrogen, oxygen, sulfur, or phosphorus). Cycloalkenyl and heterocyclic alkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocyclic alkenyl groups may be substituted with one or more groups, including (but not limited to) alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, sulfonic acid-oxo or thiol groups as described herein.

[0120] As used herein, the term "alkynyl" is a hydrocarbon group of 2 to 24 carbon atoms, having a structural formula containing at least one carbon-carbon triple bond. The alkynyl group may be unsubstituted or substituted with one or more groups, including (but not limited to) alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, sulfonic acid-oxo, or thiol.

[0121] As used herein, the term "cycloalkynyl" is a carbon-based nonaromatic ring consisting of at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include (but are not limited to) cycloheptynyl, cyclooctyynyl, cyclononynyl, etc. The term "heterocyclic alkynyl" is a type of cycloalkynyl group as defined above and is included within the meaning of the term "cycloalkynyl," wherein at least one carbon atom in the ring is replaced by a heteroatom (e.g., (but not limited to) nitrogen, oxygen, sulfur, or phosphorus). Cycloalkynyl and heterocyclic alkynyl groups can be substituted or unsubstituted. Cycloalkynyl and heterocyclic alkynyl groups can be substituted by one or more groups, including (but not limited to) alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, sulfonic acid-oxo, or thiol groups as described herein.

[0122] As used herein, the term "aryl" is a group containing any carbon-based aromatic group, including (but not limited to) benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, etc. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group in which at least one heteroatom has been incorporated into the ring. Examples of heteroatoms include (but are not limited to) nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl" is also included in the term "aryl," which defines a group containing an aromatic group that does not contain a heteroatom. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted by one or more groups, including (but not limited to) alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, sulfonic acid-oxo, or thiol. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups linked together by a fused ring structure, such as naphthalene, or linked by one or more carbon-carbon bonds, such as biphenyl.

[0123] As used herein, the term "aldehyde" is represented by the formula -C(O)H. Throughout this specification, "C(O)" is the shorthand symbol for the carbonyl group, i.e., C=O.

[0124] As used herein, the term "amine" or "amino" is derived from the formula -NA. 1 A 2 It means that A 1 and A 2 It can be independently hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl or heteroaryl as described herein.

[0125] As used herein, the term "alkylamino" is represented by the formula -NH(-alkyl), where the alkyl group is as described herein. Representative examples include (but are not limited to) methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl)amino, (tert-butyl)amino, pentylamino, isopentylamino, (tert-pentyl)amino, hexylamino, etc.

[0126] As used herein, the term "dialkylamino" is represented by the formula -N(-alkyl)2, wherein the alkyl group is as described herein. Representative examples include (but are not limited to) dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di(sec-butyl)amino, di(tert-butyl)amino, dipentylamino, diisopentylamino, di(tert-pentyl)amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, etc.

[0127] As used herein, the term "carboxylic acid" is represented by the formula -C(O)OH.

[0128] As used herein, the term "ester" is derived from the formula -OC(O)A 1 or -C(O)OA 1 It means that A 1 It can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl as described herein. As used herein, the term "polyester" is derived from formula -(A 1 O(O)CA 2 -C(O)O) a -or-(A 1 O(O)CA 2 -OC(O)) a - indicates that A 1 and A 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl group as described herein, and "a" is an integer from 1 to 500. "Polyester" is used as a term to describe a group produced by the reaction between a compound having at least two carboxylic acid groups and a compound having at least two hydroxyl groups.

[0129] As used herein, the term "ether" is derived from formula A. 1 OA 2 It means that A 1 and A 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl group as described herein. As used herein, the term "polyether" is derived from the formula -(A 1 OA 2 O) a - indicates that A 1 and A 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl group as described herein, and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutane oxide.

[0130] As used in this article, the term "halogen" or "halogen" refers to the halogens fluorine, chlorine, bromine, and iodine.

[0131] As used herein, the term "heterocyclic" refers to monocyclic and polycyclic non-aromatic ring systems and, as used herein, "heteroaryl" refers to monocyclic and polycyclic aromatic ring systems in which at least one ring member is not carbon. Terms include azacyclobutane, dioxane, furan, imidazole, isothiazole, isoxazole, morpholine, oxazole, oxazole (including 1,2,3-oxadiazole, 1,2,5-oxadiazole and 1,3,4-oxadiazole), piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine (including 1,2,4,5-tetrazine), tetrazolium (including 1,2,3,4-tetrazolium and 1,2,4,5-tetrazolium), thiadiazole (including 1,2,3-thiadiazole, 1,2,5-thiadiazole and 1,3,4-thiadiazole), thiazole, thiophene, triazine (including 1,3,5-triazine and 1,2,4-triazine), triazole (including 1,2,3-triazole and 1,3,4-triazole), etc.

[0132] As used in this article, the term "hydroxyl group" is represented by the formula -OH.

[0133] As used herein, the term "ketone" is derived from formula A. 1 C(O)A 2 It means that A 1 and A 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl group as described herein.

[0134] As used in this article, the term "azido group" is represented by the formula -N3.

[0135] As used in this article, the term "nitro" is represented by the formula -NO2.

[0136] As used in this article, the term "nitrile" is represented by the formula -CN.

[0137] As used herein, the term "silane" is derived from the formula -SiA 1 A 2 A 3 It means that A 1 A 2 and A 3 It can be independently hydrogen or alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.

[0138] As used herein, the term "sulfonic acid-oxo" is derived from the formula -S(O)A 1 -S(O)2A 1 -OS(O)2A 1 or -OS(O)2OA 1 It means that A 1It can be hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl as described herein. Throughout this specification, “S(O)” is the shorthand symbol for S=O. The term “sulfonyl” is used herein to refer to the compound of formula -S(O)₂A. 1 The sulfonic acid group-oxo group represents A. 1 It can be hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl as described herein. As used herein, the term "sulfone" is derived from formula A. 1 S(O)2A 2 It means that A 1 and A 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl group as described herein. As used herein, the term "sulfone" is derived from formula A. 1 S(O)A 2 It means that A 1 and A 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl group as described herein.

[0139] As used in this article, the term "thiol" is represented by the formula -SH.

[0140] As used in this article, "R" 1 “R” 2 “R” 3 “R” n (where n is an integer) can independently have one or more of the groups listed above. For example, if R 1 If it is a straight-chain alkyl group, one hydrogen atom in the alkyl group may optionally be replaced by a hydroxyl, alkoxy, alkyl, halogen, or other group. Depending on the chosen group, the first group may be incorporated into the second group, or alternatively, the first group may be side-attached (i.e., connected) to the second group. For example, for the phrase "alkyl group containing an amino group," the amino group may be incorporated into the alkyl backbone. Alternatively, the amino group may be attached to the alkyl backbone. The nature of the chosen group will determine whether the first group is inserted into or attached to the second group.

[0141] The compounds described herein may contain "optionally substituted" portions. Generally, the term "substituted," whether preceded by the term "optionally," means that one or more hydrogens in the specified portion are replaced by suitable substituents. Unless otherwise specified, the "optionally substituted" group may have suitable substituents at each substituted position of the group, and when more than one position in any given structure can be substituted by more than one substituent selected from the specified group, the substituents at each position may be the same or different. The substituent combinations contemplated in this disclosure preferably result in stable or chemically viable compound formations. It is also contemplated that, in some respects, unless explicitly stated to the contrary, individual substituents may be further optionally substituted (i.e., further substituted or unsubstituted).

[0142] In some respects, the structure of a compound can be represented by the following formula:

[0143] ,

[0144] It should be understood that it is equivalent to the following formula:

[0145] ,

[0146] in n Typically, it is an integer. That is, R n This can be interpreted as representing five independent substituents R. n(a) R n(b) R n(c) R n (d) R n(e) "Independent substituents" means that each R substituent can be defined independently. For example, if R... n(a) In one example, it is a halogen, then R n(b) In that example, it is not necessarily a halogen.

[0147] R is mentioned multiple times in the chemical structures and sections disclosed and described herein. 1 R 2 R 3 R 4 R 5 R 6 etc. The instruction manual mentions R... 1 R 2 R 3 R 4 R 5 R 6 Any description of etc. applies to the description of R. 1 R 2 R 3 R 4 R 5R 6 Any structure or part thereof.

[0148] The complexes disclosed herein are applicable to a wide variety of devices, including, for example, organic light-emitting diodes (OLEDs) for full-color displays and lighting applications.

[0149] This document also discloses compositions comprising one or more of the complexes disclosed herein. This disclosure provides light-emitting devices comprising one or more of the compositions described herein. This disclosure also provides a photovoltaic device comprising one or more of the complexes or compositions described herein. Additionally, this disclosure provides a light-emitting display device comprising one or more of the complexes described herein.

[0150] The complexes described herein can be used in light-emitting devices, such as OLEDs. Figure 2 A cross-sectional view of OLED 100 is depicted. OLED 100 includes a substrate 102, an anode 104, a hole transport material (HTL) 106, a light processing material 108, an electron transport material (ETL) 110, and a metal cathode layer 112. The anode 104 is typically a transparent material, such as indium tin oxide. The light processing material 108 may be an emission material (EML) comprising an emitter and a substrate.

[0151] In many aspects, Figure 2 Any one of the layers depicted may include indium tin oxide (ITO), poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), N,N'-di-1-naphthyl-N,N-diphenyl-1,1'-biphenyl-4,4'-diamine (NPD), 1,1-bis((di-4-tolylamino)phenyl)cyclohexane (TAPC), 2,6-bis(N-carbazolyl)pyridine (mCpy), 2,8-bis(diphenylphospho)dibenzothiophene (PO15), LiF, Al, or combinations thereof.

[0152] The light processing material 108 may include one or more complexes disclosed herein, optionally together with the host material. The host material may be any suitable host material known in the art. The emission color of the OLED is determined by the emission energy (optical bandgap) of the light processing material 108, which can be tuned by tuning the electronic structure of the emission complex, the host material, or both. The hole transport material in the HTL layer 106 and the electron transport material in the ETL layer 110 may both include any suitable hole transporter known in the art.

[0153] Example

[0154] The following examples are provided to fully disclose and describe to those skilled in the art how to manufacture and evaluate the complexes, compositions, articles, apparatus, and / or methods claimed herein, and are intended to be illustrative only and not to limit their scope. As much effort has been made to ensure accuracy in the figures (e.g., quantities, temperatures, etc.), but some errors and deviations should be accounted for. Unless otherwise specified, parts are parts by weight, temperatures are in °C or ambient temperature, and pressures are at or near atmospheric pressure.

[0155] The examples illustrate various methods for preparing the complexes described herein. These methods are provided to illustrate multiple preparation methods and are not intended to limit any one of the methods described herein. Therefore, those skilled in the art to which this disclosure pertains can readily modify the methods or use different methods to prepare one or more complexes described herein. The following aspects are merely illustrative and are not intended to limit the scope. Temperature, catalyst, concentration, reactant composition, and other process conditions can be varied, and those skilled in the art to which this disclosure pertains can readily select reactants and conditions suitable for the desired complex.

[0156] General procedure for Pt complexes with formulas I to VIII

[0157] Add K₂PtCl₄ (1.1 eq) and [other components] to a solution of the corresponding ligand (1 eq) in HOAc (0.02 M). n -Bu4NBr (0.1 eq). The mixture was heated to reflux and maintained for 3 days. The reaction mixture was cooled to room temperature and filtered through a short silica gel pad. The filtrate was concentrated under reduced pressure. The corresponding complex was obtained by column chromatography (hexane:DCM).

[0158] Synthesis route of PtNON-S56

[0159]

[0160] Suzuki coupling of arylboronic acid and aryl bromide

[0161] Dibenzo[b,d]thiophene-2-ylboronic acid (1.0 eq), 1,4-dibromo-2-nitrobenzene (1.1 eq), and Pd(PPh3)4 (0.08 eq) were added to an oven-dried flask. The flask was then evacuated and backfilled with nitrogen three times. Aqueous solution of K2CO3 (2 M, 3 eq) and toluene (0.2 M) were then added. The mixture was heated to 100 °C and maintained for approximately 4 hours. The mixture was cooled to room temperature and the product was separated by column chromatography (hexane:EtOAc = 20:1 to 10:1) in 60% yield.

[0162] PPh 3 Mediated reducing cyclization

[0163] 2-(4-bromo-2-nitrophenyl)dibenzo[b,d]thiophene (1.0 eq) and PPh3 (2.5 eq) were added to an oven-dried flask. The flask was then evacuated and backfilled with nitrogen three times, followed by the addition of 1,2-dichlorobenzene (0.25 M) via syringe. The mixture was heated in an oil bath at 180 °C for 12 hours. The mixture was cooled to room temperature and the product was separated by column chromatography (hexane:EtOAc = 15:1 to 8:1) in 57% yield.

[0164] Pd-catalyzed coupling of carbazole and 2-bromopyridine

[0165] Add 10-bromo-12H-benzo[4,5]thieno[3,2-a]carbazole (1 eq), 2-bromopyridine (2 eq), Pd2(dba)3 (0.05 eq), JohnPhos (0.1 eq) and [other ingredients] to an oven-dried flask. t -BuONa (1.5 eq). The flask was then evacuated and backfilled with nitrogen three times, followed by the addition of toluene (0.1 M) via syringe. The mixture was heated to reflux and maintained for 12 hours. The mixture was cooled to room temperature and the product was separated by column chromatography (hexane:EtOAc = 15:1 to 8:1) in 85% yield.

[0166]

[0167] Suzuki Coupling of Arylboronic Acids and Aryl Bromines

[0168] Dibenzo[b,d]thiophene-2-ylboronic acid (1.1 eq), 1-bromo-4-methoxy-2-nitrobenzene (1 eq), and Pd(PPh3)4 (0.08 eq) were added to an oven-dried flask. The flask was then evacuated and backfilled with nitrogen three times. Aqueous solution of K2CO3 (2 M, 3 eq) and THF (0.2 M) were then added. The mixture was heated in an oil bath at 80 °C for approximately 4 hours. The mixture was cooled to room temperature and the product was separated by column chromatography (hexane:EtOAc = 15:1 to 8:1) in 80% yield.

[0169] PPh 3 Mediated reducing cyclization

[0170] 2-(4-methoxy-2-nitrophenyl)dibenzo[b,d]thiophene (1.0 eq) and PPh3 (2.5 eq) were added to an oven-dried flask. The flask was then evacuated and backfilled with nitrogen three times, followed by the addition of 1,2-dichlorobenzene (0.25 M) via syringe. The mixture was heated in an oil bath at 180 °C for 12 hours. The mixture was cooled to room temperature and the product was separated by column chromatography (hexane:EtOAc = 10:1 to 6:1) in 62% yield.

[0171] Pd-catalyzed coupling of carbazole and 2-bromopyridine

[0172] Add 10-methoxy-12H-benzo[4,5]thieno[3,2-a]carbazole (1 eq), 2-bromopyridine (2 eq), Pd2(dba)3 (0.05 eq), JohnPhos (0.1 eq) and [other ingredients] to an oven-dried flask. t -BuONa (1.5 eq). The flask was then evacuated and backfilled with nitrogen three times, followed by the addition of toluene (0.1 M) via syringe. The mixture was heated to reflux and maintained for 12 hours. The mixture was cooled to room temperature and the product was separated by column chromatography (hexane:EtOAc = 10:1 to 6:1) in 83% yield.

[0173] 10-Methoxy-12-(pyridin-2-yl)-12H-benzo[4,5]thieno[3,2-a]carbazole demethylation

[0174] An aqueous solution of HBr (48 wt%, 10 eq) was added to a solution of 10-methoxy-12-(pyridin-2-yl)-12H-benzo[4,5]thieno[3,2-a]carbazole in acetic acid (0.1 M). The mixture was heated in an oil bath at 120 °C for 12 h. The mixture was cooled to room temperature and then water (equal to the volume of acetic acid) was added. The mixture was neutralized to pH 5–6 with solid K₂CO₃. The precipitate was collected by filtration, washed three times with water, and dried under reduced pressure. The yield was quantitative.

[0175] CuI-catalyzed synthesis of NON-S56 ligand

[0176] Fg. 1 (1.2 eq), CuI (0.1 eq), 2-pyridinecarboxylic acid (0.2 eq), and K3PO4 (2 eq) were added to a solution of 12-(pyridin-2-yl)-12H-benzo[4,5]thieno[3,2-a]carbazole-10-ol (1 eq) in DMSO (0.1 M). The mixture was heated to reflux and maintained for 24 hours. The mixture was cooled to room temperature. Water (3 times the volume of DMSO) was then added. The mixture was extracted three times with EtOAc. The combined organic phases were then concentrated. The NON-S56 ligand was purified by column chromatography (hexane:EtOAc = 8:1 to 3:1).

[0177] Synthesis of PtNON-S56

[0178] Add K₂PtCl₄ (1.1 eq) and K₂PtCl₄ to a solution of NON-S56 ligand (1 eq) in HOAc (0.02 M) n -Bu4NBr (0.1 eq). The mixture was heated to reflux and maintained for 3 days. The reaction mixture was cooled to room temperature and filtered through a short silica gel pad. The filtrate was concentrated under reduced pressure. Purification by column chromatography (hexane:DCM = 1:2 to 1:3) gave PtNON-S56 in 59% yield.

[0179] A general program for Pt complexes with the general formula IX

[0180] Add K₂PtCl₄ (1.1 eq) and [other components] to a solution of the corresponding ligand (1 eq) in 2-ethoxyethanol (0.02 M). n -Bu4NBr (0.1 eq). The mixture was heated to reflux and maintained for 3 days. The reaction mixture was cooled to room temperature and filtered through a short silica gel pad. The filtrate was concentrated under reduced pressure. The corresponding complex was obtained by column chromatography (hexane:DCM).

[0181] Example 1. Synthesis route of Pt3O3

[0182]

[0183] Synthesis of 2-(3-bromophenyl)pyridine

[0184] Add (3-bromophenyl)boric acid (1.1 eq), 2-bromopyridine (1 eq), Pd(PPh3)4 (0.1 eq), EtOH / H2O (3:3:1 ratio, EtOH 0.2 M), and K2CO3 aqueous solution (2 M, 10 eq) to an oven-dried flask. Heat the mixture in an oil bath at 80 °C for 24 hours. Cool the mixture to room temperature. Then remove the solvent under reduced pressure. Separate the product by column chromatography (hexane:EtOAc = 15:1 to 8:1), with a yield of 88%.

[0185] Synthesis of 2-(3-methoxyphenyl)pyridine

[0186] Add (3-methoxyphenyl)boric acid (1.1 eq), 2-bromopyridine (1 eq), Pd(PPh3)4 (0.1 eq), EtOH / H2O (3:3:1 ratio, EtOH 0.2 M), and K2CO3 aqueous solution (2 M, 10 eq) to an oven-dried flask. Heat the mixture in an oil bath at 80 °C for 24 hours. Cool the mixture to room temperature. Then remove the solvent under reduced pressure. The product was separated by column chromatography (hexane:EtOAc = 10:1 to 6:1) in 93% yield.

[0187] Synthesis of 3-(pyridin-2-yl)phenol

[0188] An aqueous solution of HBr (48 wt%, 10 eq) was added to a solution of 2-(3-methoxyphenyl)pyridine (1 eq) in acetic acid (0.1 M). The mixture was heated in an oil bath at 120 °C for 12 hours. The mixture was cooled to room temperature and then water (equal to the volume of acetic acid) was added. The mixture was neutralized to pH 5–6 with solid K₂CO₃. The precipitate was collected by filtration, washed three times with water, and dried under reduced pressure. The yield was quantitative.

[0189] Synthesis of 3O3 ligands

[0190] The mixture was heated to reflux and maintained for 24 hours. The mixture was then cooled to room temperature. Water (3 times the volume of DMSO) was then added. The mixture was extracted three times with EtOAc. The combined organic phases were then concentrated. Purification by column chromatography (hexane:EtOAc = 8:1 to 3:1) yielded the 3O3 ligand in 85% yield.

[0191] Synthesis of Pt3O3

[0192] Add K2PtCl4 (1.1 eq) and 3O3 ligand (1 eq) to a solution of EtOCH2CH2OH (0.02 M). n -Bu4NBr (0.1 eq). The mixture was heated to reflux and maintained for 3 days. The reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Water was then added, and the precipitate was filtered and washed three times with water. The collected precipitate was then dried to give the crude product in quantitative yield.

[0193] Example 2. Synthetic route of Pt3O3-dtb

[0194]

[0195] Synthesis of 3,3'-oxybis(bromobenzene)

[0196] CuI (0.1 eq), 2-pyridinecarboxylic acid (0.2 eq), K3PO4 (2 eq), and 1,3-dibromobenzene (3 eq) were added to a solution of 3-bromophenol (1 eq) in DMSO (0.5 M). The mixture was heated in an oil bath at 100 °C for 24 hours. The mixture was then cooled to room temperature. Water (3 times the volume of DMSO) was then added. The mixture was extracted three times with EtOAc. The combined organic phases were then concentrated. The product was purified by column chromatography (hexane) to a 55% yield.

[0197] 2,2'-(oxybis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentane) synthesis

[0198] To a solution of 3,3'-oxybis(bromobenzene) (1 eq) in dioxane (0.2 M), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborhecyclopentane) (3 eq), Pd(dppf)Cl2·DCM (0.1 eq), and KOAc (4 eq) were added. The mixture was heated in an oil bath at 80 °C for 24 hours. The mixture was then cooled to room temperature. The solvent was then removed under reduced pressure. The product was separated by column chromatography (hexane:EtOAc = 50:1 to 10:1) in 70% yield.

[0199] Synthesis of 3O3-dtb ligands

[0200] Add 2,2'-(oxybis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentane) (1 eq), 2-bromo-4-(tert-butyl)pyridine (2.4 eq), Pd(PPh3)4 (0.1 eq), EtOH / H2O (2:1 ratio, 0.2 M), and an aqueous solution of K2CO3 (2 M, 10 eq) to an oven-dried flask. Heat the mixture in an oil bath at 80 °C for 24 hours. Cool the mixture to room temperature. Then remove the solvent under reduced pressure. The product was separated by column chromatography (hexane:EtOAc = 10:1 to 4:1) in 64% yield.

[0201] Synthesis of Pt3O3-dtb

[0202] Add K2PtCl4 (1.1 eq) and 3O3-dtb ligand (1 eq) to a solution of HOAc (0.02 M) to a solution of HOAc (0.02 M). n -Bu4NBr (0.1 eq). The mixture was heated to reflux and maintained for 3 days. The reaction mixture was cooled to room temperature and filtered through a short silica gel pad. The filtrate was concentrated under reduced pressure. Purification by column chromatography (hexane:DCM = 1:2 to 1:3) gave Pt3O3-dtb in 68% yield.

[0203] Figure 3 The emission spectra of Pt3O3-dtb in dichloromethane are shown at 77 K and room temperature.

Claims

1. A complex compound represented by the general formula IX: ， General formula IX in: Ar 1 Ar 2 Ar 3 and Ar 4 Each individually represents an aryl, heteroaryl, fused aryl, or fused heteroaryl group having 5 to 10 ring atoms; R 1 R 2 R 3 and R 4 Each can independently represent hydrogen, deuterium, trideuterium methyl, pentadeuterium phenyl, halogen, hydroxyl, nitro, nitrile, thiol; or substituted or unsubstituted alkoxy, aryl, amino, or C1-C4 alkyl. Each n independently represents an integer that the valence number is allowed; Y 1a Y 1b Y 1c Y 2a Y 2b Y 2c Y 2d Y 3a Y 3b Y 3c Y 3d Y 4a Y 4b and Y 4c Each can independently represent C, N, Si, O, or S; X represents O, S, NR, CRR', SiRR', PR, BR, S=O, O=S=O, Se, Se=O or O=Se=O, wherein each R and R' independently represents hydrogen, deuterium, trideuterium methyl, pentadeuterium phenyl, hydroxyl, nitro, nitrile, thiol, or substituted or unsubstituted alkoxy, aryl, amino or C1-C4 alkyl; L 1 and L 2 Each may or may not exist independently, and if present, each independently represents an alkyl, alkoxy, alkenyl, alkynyl, hydroxyl, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, or heterocyclic linking group.

2. The complex according to claim 1, wherein Ar 1 Ar 2 Ar 3 and Ar 4 Independently, it is phenyl, pyridyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, naphthyl, benzimidazolyl, quinazolinyl, or quinolinyl.

3. The complex according to claim 1, wherein the complex is represented by one of the following structures, wherein: Every Z that exists 1 Z 2 Z 3 and Z 4 Independently represent C or N; and Every existing R 5 and R 6 Independently representing hydrogen, deuterium, trideuterium methyl, halogen, hydroxyl, nitro, nitrile, thiol; or substituted or unsubstituted alkoxy, aryl, amino, pentadeuterium phenyl, or C1-C4 alkyl; and Each n independently represents an integer that the valence number is allowed. 。 4. The complex according to claim 1, wherein the complex is represented by one of the following structures, and wherein each R and R', if present, independently represents a substituted or unsubstituted alkoxy, aryl, heteroaryl, or C1-C4 alkyl group: 。 。 5. An organic light-emitting diode comprising the complex according to claim 1.

6. A light-emitting device comprising an organic light-emitting diode according to claim 5.

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