A tetradentate platinum complex and light emitting device

Abstract

This application discloses a tetradentate platinum complex and a light-emitting device. The general structural formula of the tetradentate platinum complex is shown in one of the following formulas: Formula (1) Formula (2); wherein, ring A, ring B, ring C and ring D are independently selected from substituted or unsubstituted benzene rings and substituted or unsubstituted naphthalene rings, respectively; X1~X4 are independently selected from N or CR a Ar1 is selected from substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl groups. This tetradentate platinum complex exhibits excellent optical and electrical stability, achieves high luminous efficiency at low driving voltages, and significantly extends device lifespan, making it suitable as a high-performance luminescent material for light-emitting devices. By introducing a carbazole-based seven-membered ring structure into its ligands, it unexpectedly demonstrates comprehensive advantages in device performance. This class of compounds provides the light-emitting device industry with highly efficient and stable luminescent materials with application potential.

Description

Technical Field

[0001] This application relates to the field of organic electroluminescence technology, specifically to a tetradentate platinum complex and a light-emitting device. Background Technology

[0002] As a new generation of display and lighting technology, light-emitting devices (LEDs) have received increasing attention and have broad application prospects. However, compared with market application demands, LEDs still need further optimization in terms of luminous efficiency, driving voltage, and lifespan.

[0003] Typical light-emitting devices employ a multilayer structure similar to a "sandwich," where various functional organic thin films are deposited between two metal electrodes. Driven by an applied voltage, holes and electrons are injected from the anode and cathode, respectively, migrate to the light-emitting layer, recombine to form excitons, and release energy as light or heat during deexcitation, thus achieving light emission. The luminous efficiency and stability of light-emitting devices largely depend on the performance of the luminescent materials used. Early fluorescent light-emitting devices could only utilize singlet excitons for emission, while triplet excitons, which account for approximately 75% of the total excitons, typically dissipate through non-radiative relaxation, limiting the improvement of device efficiency. In 1998, Professor Zhiming Zhi's team at the University of Hong Kong and Thompson et al. reported the use of transition metal complexes to achieve phosphorescence emission from triplet excitons, significantly improving exciton utilization. Phosphorescent light-emitting devices can utilize both singlet and triplet excitons simultaneously, theoretically achieving 100% internal quantum efficiency, which has strongly promoted the commercialization of light-emitting devices.

[0004] By controlling the molecular structure of luminescent materials, the color of light emitted by light-emitting devices can be precisely adjusted. Devices can be designed with single or multiple luminescent layers to meet target spectral requirements. Currently, phosphorescent materials in green, yellow, and red colors have been commercially applied. In commercial full-color light-emitting displays, a combination of blue fluorescent materials and yellow, green, and red phosphorescent materials is typically used. However, developing novel luminescent materials that combine high efficiency and long lifespan remains a crucial challenge for the industry.

[0005] In the development of related materials, patent document CN117903209A discloses a series of blue phosphorescent tetradentate coordination compounds based on carbazole end groups extended with phenyl groups to form seven-membered rings. These compounds can serve as blue phosphorescent guest materials, but their device efficiency still needs improvement. Another patent, CN115611949A, reports a class of carbazole-carbazole linked tetradentate platinum complexes, but their device performance, especially their operating life, still falls short of practical application requirements. Therefore, existing material systems still need further optimization and innovation to achieve higher device efficiency and longer lifespan. Summary of the Invention

[0006] This application aims to address at least one of the technical problems existing in the prior art. To this end, this application proposes a tetradentate platinum complex that, when used in light-emitting devices, exhibits both high device efficiency and a long lifespan.

[0007] This application also proposes a light-emitting device made using the above-mentioned tetradentate platinum complex.

[0008] According to one aspect of this application, a tetradentate platinum complex is proposed, the general structural formula of which is shown in formula (1) or formula (2): Equation (1) Equation (2) Among them, ring A, ring B, ring C and ring D are independently selected from substituted or unsubstituted benzene rings or substituted or unsubstituted naphthalene rings; X1~X4 are independently selected from N or CR a ; R a Selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboron, C6-C60 arylboron, C6-C60 arylphosphine, C6-C60 arylamino, or substituted or unsubstituted C6-C60 aryl, with two adjacent R a They can be connected to form a parallel loop; R1, R2, and R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphinyl, C6-C60 arylamino, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C1-C40 alkyl. a and b represent integers from 0 to 4; c represents integers from 0 to 3; Ar1 is selected from substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C3-C60 heteroaryl; The substitutions in ring A, ring B, ring C, and ring D are each independently represented by at least one of deuterium, halogen, cyano, isocyano, phosphinyl, halo-C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amino, deuterium-substituted or unsubstituted C1-C10 alkyl, C1-C6 alkyl-substituted or unsubstituted C6-C30 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C30 heteroaryl, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions; The substitution in Ar1 means that it is substituted by at least one of deuterium, halogen, cyano, isocyano, phosphin, halo-C1-C6 alkyl, C3-C16 cycloalkyl, deuterium-substituted or unsubstituted C1-C10 alkyl or C1-C6 alkyl-substituted amino group, and the number of substitutions is from monosubstituted to the maximum number of substitutions. The R a The substitutions in R1, R2, and R3 independently represent substitution by at least one of deuterium, halogen, cyano, isocyano, phosphin, halogenated C1-C6 alkyl, C3-C16 cycloalkyl, deuterium-substituted or unsubstituted C1-C10 alkyl, or C1-C6 alkyl-substituted amino group, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions; the heteroatoms in the heteroalkyl, heterocycloalkyl, and heteroaryl groups are independently selected from at least one of O, S, N, P, B, Si, Ge, or Se.

[0009] The tetradentate platinum complexes according to embodiments of this application have at least the following beneficial effects: The tetradentate platinum complexes of this application possess excellent optical and electrical stability, can achieve high luminous efficiency at lower driving voltages, and significantly extend device lifespan, making them suitable as high-performance luminescent materials for use in light-emitting devices. By introducing a carbazole-based seven-membered ring structure into its ligands, it unexpectedly exhibits comprehensive advantages in device performance. This type of novel compound provides the light-emitting device industry with highly efficient and stable luminescent materials with application potential.

[0010] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0011] Figure 1 This is the proton NMR spectrum of compound A123 obtained in the embodiments of this application.

[0012] Figure 2 This is a schematic diagram of the structure of the light-emitting device in Embodiment 1 of this application. Detailed Implementation

[0013] To enable those skilled in the art to more clearly understand the technical solutions described in this application, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed in this application.

[0014] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0015] The first aspect of this application provides a tetradentate platinum complex.

[0016] Specifically, the general structural formula of this complex is shown in one of the following equations: Equation (1) Equation (2) Among them, ring A, ring B, ring C and ring D are independently selected from substituted or unsubstituted benzene rings or substituted or unsubstituted naphthalene rings; X1~X4 are independently selected from N or CR a ; R a Selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboron, C6-C60 arylboron, C6-C60 arylphosphine, C6-C60 arylamino, or substituted or unsubstituted C6-C60 aryl, with two adjacent R a They can be connected to form a parallel loop; R1, R2, and R3 are each independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphinyl, C6-C60 arylamino, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C1-C40 alkyl. a and b represent integers from 0 to 4; c represents integers from 0 to 3; Ar1 is selected from substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C3-C60 heteroaryl; The substitutions in ring A, ring B, ring C, and ring D are each independently represented by at least one of deuterium, halogen, cyano, isocyano, phosphinyl, halogenated C1-C6 alkyl, C3-C16 cycloalkyl, deuterium-substituted or unsubstituted C1-C10 alkyl, C1-C6 alkyl-substituted amino, C1-C6 alkyl-substituted or unsubstituted C6-C30 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C30 heteroaryl, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions; The substitution in Ar1 means that it is substituted by at least one of deuterium, halogen, cyano, isocyano, phosphin, halo-C1-C6 alkyl, C3-C16 cycloalkyl, deuterium-substituted or unsubstituted C1-C10 alkyl or C1-C6 alkyl-substituted amino group, and the number of substitutions is from monosubstituted to the maximum number of substitutions. The R a The substitutions in R1, R2 and R3 independently represent substitution by at least one of deuterium, halogen, cyano, isocyano, phosphin, halo-C1-C6 alkyl, C3-C16 cycloalkyl, deuterium-substituted or unsubstituted C1-C10 alkyl or C1-C6 alkyl-substituted amino groups, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions; The heteroatoms in the heteroalkyl, heterocycloalkyl, and heteroaryl groups are each independently selected from at least one of O, S, N, P, B, Si, Ge, or Se.

[0017] In some embodiments, the structural formula of the tetradentate platinum complex is selected from one of the following general formulas:

[0018]

[0019] Among them, Y1~Y9 and Z1~Z9 are each independently CR b ; R b Each is independently selected from at least one of hydrogen, deuterium, halogen, cyano, isocyano, phosphinyl, halogenated C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amino, deuterated or unsubstituted C1-C6 alkyl, C1-C6 alkyl-substituted or unsubstituted C6-C30 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C30 heteroaryl.

[0020] In some implementations, R b Each is independently selected from at least one of hydrogen, deuterium, halogen, cyano, isocyano, phosphinyl, halogenated C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amino, deuterated or unsubstituted C1-C6 alkyl, C1-C6 alkyl-substituted or unsubstituted C6-C20 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C20 heteroaryl.

[0021] In some implementations, R b Each is independently selected from at least one of hydrogen, deuterium, halogen, cyano, isocyano, phosphinyl, halogenated C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amino, deuterated or unsubstituted C1-C6 alkyl, C1-C6 alkyl-substituted or unsubstituted C6-C10 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C10 heteroaryl.

[0022] In some embodiments, the tetradentate platinum complex contains at least one deuterium atom.

[0023] In some embodiments, the substitutions in ring A, ring B, ring C, and ring D independently represent substitution by at least one of deuterium, halogen, cyano, isocyano, phosphinyl, halogenated C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl-substituted amino, deuterium-substituted or unsubstituted C1-C6 alkyl, C1-C6 alkyl-substituted or unsubstituted C6-C20 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C20 heteroaryl, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions.

[0024] In some embodiments, the substitutions in ring A, ring B, ring C, and ring D independently represent substitution by at least one of deuterium, halogen, cyano, isocyano, phosphinyl, halo-C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl-substituted amino, deuterium-substituted or unsubstituted C1-C6 alkyl, C1-C6 alkyl-substituted or unsubstituted C6-C10 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C10 heteroaryl, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions.

[0025] In some embodiments, the substitutions in Ar1 independently represent substitution by at least one of deuterium, halogen, cyano, isocyano, phosphin, halogenated C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl-substituted amino group or deuterium-substituted or unsubstituted C1-C6 alkyl group, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions.

[0026] In some embodiments, the substitutions in ring A, ring B, ring C, ring D and Ar1 independently represent substitution by at least one of deuterium, halogen, cyano, isocyano, phosphino, or deuterium-substituted or unsubstituted C1-C6 alkyl groups, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions.

[0027] In some embodiments, the heteroatoms in the heteroalkyl and heterocyclic alkyl groups are each independently selected from at least one of O, B, Si, Ge, or Se.

[0028] In some embodiments, the heteroatom in the heteroaryl group is selected from at least one of O, S, or N.

[0029] In some embodiments, the Ar1 is selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C2-C30 heteroaryl.

[0030] In some embodiments, the Ar1 is selected from substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C6-C20 aryl groups, or substituted or unsubstituted C2-C20 heteroaryl groups.

[0031] In some embodiments, the Ar1 is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C12 aryl, or substituted or unsubstituted C2-C12 heteroaryl.

[0032] In some embodiments, Ar1 is selected from substituted or unsubstituted methyl, substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted fluoranyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, or a combination of at least two of the above.

[0033] In some embodiments, the Ar1 is a combination of two substances, including at least one of the following: a combination of a substituted or unsubstituted phenyl group with a substituted or unsubstituted pyridinyl group; a combination of a substituted or unsubstituted phenyl group with a substituted or unsubstituted carbazole group; a combination of a substituted or unsubstituted phenyl group with a substituted or unsubstituted terphenyl group; and a combination of a substituted or unsubstituted phenyl group with a substituted or unsubstituted diphenyl group. The combination can be a single combination or a double combination. For example, a substituted or unsubstituted phenyl group simultaneously combined with two substituted or unsubstituted pyridinyl groups forms a meta-(4-pyridyl)phenyl group; another example is a substituted or unsubstituted phenyl group simultaneously combined with two substituted or unsubstituted terphenyl groups. ; or substituted or unsubstituted phenyl groups simultaneously combined with two substituted or unsubstituted diphenyl groups to form substituted or unsubstituted phenyl groups. .

[0034] In some embodiments, the Ar1 is selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C6-C30 heteroaryl, wherein the substitution means being substituted by at least one of deuterium, halogen, cyano, isocyano, phosphin or C1-C6 alkyl, and the number of substitutions is from monosubstituted to the maximum number of substitutions, and the heteroatom in the heteroaryl is O.

[0035] In some implementations, at least one of X1 to X4 is N.

[0036] In some implementations, one, two, or three of X1 to X4 are N.

[0037] In some implementations, X4 is N.

[0038] In some implementations, R a Selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphinyl, C6-C30 arylamino, or substituted or unsubstituted C6-C30 aryl, with two adjacent R a They can be connected to form a parallel loop.

[0039] In some implementations, R a Selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C10 alkyl, C1-C10 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C5-C20 heteroaryl, C1-C10 alkoxy, C6-C20 aryloxy, C3-C10 alkylsilyl, C6-C20 arylsilyl, C1-C10 alkylboryl, C6-C20 arylboryl, C6-C20 arylphosphinyl, C6-C20 arylamino, or substituted or unsubstituted C6-C20 aryl, with two adjacent R a They can be connected to form a parallel loop.

[0040] In some embodiments, R1, R2, and R3 are each independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphinyl, C6-C30 arylamino, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C1-C20 alkyl.

[0041] In some embodiments, R1, R2, and R3 are each independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, C1-C10 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C5-C20 heteroaryl, C1-C10 alkoxy, C6-C20 aryloxy, C3-C10 alkylsilyl, C6-C20 arylsilyl, C1-C10 alkylboryl, C6-C20 arylboryl, C6-C20 arylphosphinyl, C6-C20 arylamino, substituted or unsubstituted C6-C20 aryl, or substituted or unsubstituted C1-C10 alkyl.

[0042] In some embodiments, R1, R2, and R3 are each independently selected from at least one of deuterium, halogen, cyano, nitro, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C5-C40 heteroaryl, C1-C20 alkoxy, C6-C20 aryloxy, deuterium-substituted or unsubstituted C1-C20 alkyl, or C1-C6 alkyl-substituted or unsubstituted C6-C40 aryl.

[0043] In some embodiments, R1, R2, and R3 are each independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, C1-C10 heteroalkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C5-C20 heteroaryl, C1-C10 alkoxy, C6-C12 aryloxy, C1-C6 alkyl-substituted or unsubstituted C6-C20 aryl, or deuterium-substituted or unsubstituted C1-C10 alkyl.

[0044] In some embodiments, R1, R2, and R3 are each independently selected from at least one of deuterium, halogen, cyano, nitro, C1-C6 alkyl, C5-C10 heteroaryl, C1-C6 alkoxy, C6-C10 aryl, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, C1-C6 alkyl-substituted or unsubstituted C6-C10 aryl, or deuterium-substituted or unsubstituted C1-C6 heteroalkyl.

[0045] In some implementations, R a The substitutions in the aryl groups substituted in R1, R2, or R3 are each independently selected from at least one of deuterium, cyano, halogen, deuterated C1-C6 alkyl, halo-C1-C6 alkyl, or C1-C6 alkyl.

[0046] In some embodiments, the substitutions in the alkyl groups substituted in R1, R2, or R3 are each independently selected from at least one of deuterium, cyano, halogen, deuterated C1-C6 alkyl, halogenated C1-C6 alkyl, or C1-C6 alkyl.

[0047] In some embodiments, the general structural formula of the tetradentate platinum complex is shown in formula (1), wherein ring A and ring B are independently selected from substituted or unsubstituted benzene rings or substituted or unsubstituted naphthalene rings, Ar1 is selected from C6 to C30 aryl groups substituted or unsubstituted with C1-C10 alkyl groups; X1 to X3 are all CH, X4 is selected from N or CH; R2 is selected from C1-C10 alkyl groups; a and c represent 0, and b represents an integer from 0 to 2; wherein the substitution in ring A and ring B independently represents substitution by at least one of deuterium, halogen, cyano, isocyano, phosphin or C1-C10 alkyl groups, and the number of substitutions ranges from monosubstituted to the maximum number of substitutions.

[0048] In some embodiments, the general structural formula of the tetradentate platinum complex is shown in formula (1), wherein ring A and ring B are independently selected from substituted or unsubstituted benzene rings or substituted or unsubstituted naphthalene rings, Ar1 is selected from C1-C6 alkyl substituted or unsubstituted phenyl; X1 to X3 are all CH, X4 is selected from N or CH; R2 is selected from C1-C10 alkyl; a and c represent 0, and b represents an integer from 0 to 2; wherein the substitution in ring A and ring B is independently represented by substitution by at least one of deuterium, halogen, cyano, isocyano, phosphin or C1-C10 alkyl, and the number of substitutions is from monosubstituted to the maximum number of substitutions.

[0049] In some embodiments, the general structural formula of the tetradentate platinum complex is shown in formula (1), wherein ring A and ring B are independently selected from benzene ring or naphthalene ring, Ar1 is selected from C1-C6 alkyl substituted or unsubstituted phenyl; X1~X3 are all CH, X4 is selected from N or CH; R2 is selected from C1-C10 alkyl; a and c represent 0, b represents 1, and the number of substitutions ranges from monosubstituted to the maximum number of substitutions.

[0050] In some embodiments, the tetradentate platinum complex has the general structural formula shown in formula (1), wherein ring A and ring B are independently selected from benzene rings or naphthalene rings, Ar1 is selected from C1-C6 alkyl-substituted or unsubstituted phenyl groups; X1~X3 are all CH, X4 is selected from N or CH; R2 is selected from C1-C6 alkyl groups; a and c represent 0, b represents 1, and the number of substitutions ranges from monosubstituted to the maximum number of substitutions. In some embodiments, the alkyl group is methyl, isopropyl, or tert-butyl.

[0051] In some embodiments, the compound is one of the following structural formulas, or a structure in which hydrogen is partially or completely replaced by deuterium or fluorine:

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[0095] .

[0096] The second aspect of this application provides for the application of the aforementioned tetradentate platinum complex.

[0097] Specifically, a light-emitting device comprises the aforementioned tetradentate platinum complex.

[0098] In some embodiments, a light-emitting device includes a cathode and an anode, with an organic layer between the cathode and the anode, the organic layer comprising the aforementioned tetradentate platinum complex.

[0099] In some embodiments, the organic layer includes a light-emitting layer comprising the tetradentate platinum complex.

[0100] In some embodiments, the luminescent layer is a red or orange luminescent layer. The aforementioned complex serves as a red or orange luminescent guest material.

[0101] definition Unless otherwise stated, the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art. However, for a better understanding of this application, definitions of some terms are provided below. In the event that the definitions of terms provided herein differ from the meanings commonly understood by those skilled in the art, the definitions and interpretations provided herein shall prevail.

[0102] It should be noted that in this instruction manual, " "" indicates the connection site with other groups.

[0103] As used herein, the term “and / or” means the presence or use of the listed items, either alone or in combination. In practice, the term means the use or presence of “at least one” or “one or more” of the listed items.

[0104] "Two adjacent R" a "Can be linked to form a ring" means that when two adjacent carbon atoms on the benzene ring containing X1~X4 are connected to R a They can be interconnected through chemical bonds and share adjacent carbon atoms, thus forming a fused bicyclic system, also known as a fused ring (or fused ring). "Two adjacent R..." b The meaning is similar to "can be connected to form a ring".

[0105] The term "multiple" refers to a quantity greater than or equal to 2, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0106] "Halogen" refers to fluorine, chlorine, bromine, or iodine.

[0107] "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. The number of carbon atoms can be C1-C60, C1-C40, C1-C30, C1-C20, C1-C12, C1-C10, C1-C6, or C1-C4. Non-limiting examples include methyl, ethyl, propyl, butyl, heptyl, and decyl. Each group includes various isomers; for example, butyl includes n-butyl, isobutyl, sec-butyl, and tert-butyl isomers.

[0108] "Cycloalkyl" refers to an alkyl group with a cyclic structure, which can include monocyclic, polycyclic, and spiroalkyl groups. The number of carbon atoms can be C3-C60, C3-C40, C3-C30, C3-C20, C3-C12, C3-C10, or C3-C6. Non-limiting examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, and 2-norbornyl.

[0109] "Alkenyl" refers to a hydrocarbon containing at least one unsaturated carbon-carbon double bond. The number of carbon atoms can be C2-C40, C2-C30, C2-C20, C2-C12, C2-C10, C2-C6, or C2-C4. Non-limiting examples include: vinyl, propenyl, allyl, butadienyl, hextrienyl, etc.

[0110] "Alynyl" refers to a hydrocarbon containing at least one unsaturated carbon-carbon triple bond. The number of carbon atoms can be C2-C40, C2-C30, C2-C20, C2-C12, C2-C10, C2-C6, or C2-C4. Non-limiting examples include ethynyl and propynyl.

[0111] "Heteroalkyl" refers to an alkyl group in which at least one carbon atom is replaced by a non-carbon atom, excluding cases where the carbon atom serving as a linking site is replaced by a non-carbon atom (e.g., alkoxy, alkylsilyl). The number of carbon atoms can be C1-C40, C1-C30, C1-C20, C1-C12, C1-C10, C1-C6, or C1-C4. Examples include mercaptomethylmethane, methoxymethane, ethoxymethane, tert-butoxymethane, and N,N-dimethylmethane.

[0112] "Heterocyclic alkyl" refers to a cycloalkyl group in which at least one carbon atom of the ring is replaced by a non-carbon atom, which can be selected from at least one of O, S, N, P, B, Si, Ge, or Se. The number of carbon atoms in the ring can be C3-C40, C3-C30, C3-C20, C3-C12, C3-C10, or C3-C6. Non-limiting examples include epoxide butyl, epoxide pentyl, and epoxide hexyl.

[0113] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl or polycyclic aryl. At least one ring in a polycyclic aryl compound is an aromatic ring system. Multiple rings in a polycyclic aryl compound can be linked together by single bonds or can be fused together, for example, phenyl fusion with phenyl to form naphthyl, or phenyl fusion with phenyl to form diphenyl. The number of carbon atoms can be C6~C60, C6-C30, C6~C20, C6~C12, or C6~C10. Non-limiting examples include phenyl, naphthyl, anthracene, phenanthrene, tetraphenyl, pyrene, dinaphthylphenyl, acenaphthyl, benzo[g]pyrene, benzo[g]phenanthrene, benzo[g]triylyl, fluorenyl, spirodifluorenyl, 9,9-dimethylfluorenyl, benzo[g]fluorenyl, dibenzo[g]fluorenyl, diphenyl, triphenyl, tetraphenyl, and fluoranyl, etc. Benzophenanthrene groups include 1,2-benzophenanthrene, 3,4-benzophenanthrene, 9,10-benzophenanthrene, etc.

[0114] "Heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom. It can be a monocyclic or polycyclic heteroaryl group. In a polycyclic heteroaryl group, multiple rings can be linked together by single bonds or fused together, with at least one carbon atom on at least one ring being replaced by a non-carbon atom. For example, a phenyl group fused with a carbazole group forms a benzocarbazole group, or a phenyl group linked with a carbazole group by a single bond forms a phenyl-substituted carbazole group or a carbazole-substituted phenyl group. The non-carbon atom can be a monovalent group selected from heterocyclic aromatic systems of O, S, N, Se, Si, or Ge, but does not include cases where the aryl group uses a non-carbon atom as a linking site (e.g., aryloxy, arylsilyl, arylamino). The number of carbon atoms can be C3-C30, C3-C20, C3-C12, C3-C10, or C3-C6. Non-limiting examples include: pyrrolo, pyrrolopyrrolo, furanopyrrolo, thienopyrrolo, pyridyl, pyrazolyl, pyrimidinyl, pyrazinyl, triazinyl, pyridazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, indoleyl, isoindoleyl, indoleazolyl, imidazolyl, benzimidazolyl, triazolyl, tetrazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, furanofuranyl, azadibenzofuranyl, thienofuranyl, diazadibenzofuranyl, benzo[B]naphtho[1,2] -D] furanyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, quinazolinoneyl, carbazoyl, azacarbazoyl, diazacarbazoyl, phenanthrynyl, primidyl, acridineyl, dihydroacridyl, phenanthrynyl, oxazolinyl, oxazolyl, oxadiazolyl, benzoisooxazolyl, thiazoyl, benzothiazoyl, benzoisothiazoyl, pyrroloimidazoyl, furazolyl, thienyl, benzothiaphenyl, dibenzothiaphenyl, azadibenzothiaphenyl, diazadibenzothiaphenyl, thienothiaphenyl and o-diazanaphthyl, etc.

[0115] "Alkoxy" refers to a group having an "O-alkyl" structure, that is, an alkyl group as defined above is attached to the parent nucleus via an oxygen atom. Non-limiting examples include: methoxy, ethoxy, and tert-butoxy (-OC(CH3)3 or -OtBu), etc.

[0116] "Aryloxy group" refers to a group having an "O-aryl" structure, that is, an aryl group as defined above is attached to the parent nucleus via an oxygen atom. Non-limiting examples of aryloxy groups include phenoxy, naphthoxy, or biphenyloxy groups.

[0117] "Arylamine" refers to an amino group substituted with an aryl group, where "aryl" is defined as previously stated. The number of carbon atoms in an alkylamine group can be C6-C20, C0-C12, C0-C10, C0-C6, or C0-C4. When the alkylamine group is C0, i.e., has 0 carbon atoms, it represents an -NH2 group. Other non-limiting examples of alkylamine groups include: methylamino, ethylamino, dimethylaminotriethylammonium diisopropylamino, and trimethylammonium.

[0118] In expressions such as "the R group of substituted or unsubstituted Ca-Cb", "Ca-Cb" refers to the number of carbon atoms a to b when the R group is unsubstituted, excluding the number of carbon atoms in the substituents when the R group is substituted.

[0119] "Substitution" in "substituted or unsubstituted" means that one or more hydrogen atoms are replaced by other atoms or groups, and unless otherwise defined, it also includes the replacement of one or more hydrogen atoms by groups formed by the connection of two or more of the substituents described above.

[0120] "Maximum number of substitutions" refers to the maximum number of hydrogen atoms contained in the group when there are no substituents other than hydrogen.

[0121] "At least two combinations" means that at least two defined groups are connected by a single bond or fused together. For example, phenyl groups fused together to form a naphthyl group, or phenyl groups connected by a single bond to form a diphenyl group. It should be understood that the combination of groups is contingent upon satisfying the defined range of carbon numbers.

[0122] The following embodiments are merely for the purpose of understanding the technical invention and should not be regarded as specific limitations of this application.

[0123] The raw materials and solvents used in the synthesis of the compounds in this application were all purchased from suppliers well-known to those skilled in the art, such as Alfa and Acros.

[0124] Synthesis of compound A6

[0125] Synthesis of compound A6-3 Compound A6-1 (35.00 g, 205.95 mmol), compound A6-2 (44.27 g, 187.22 mmol), palladium dichloride (1.31 g, 1.87 mmol), potassium carbonate (64.69 g, 468.06 mmol), toluene (350 mL), ethanol (70 mL), and deionized water (70 mL) were added to a 1000 mL three-necked round-bottom flask. The flask was purged with nitrogen three times. The system was then heated to 90 °C and reacted for 5 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 10:1 as the developing solvent). Compound A6-2 was completely consumed.

[0126] The sample was cooled to 60°C, concentrated under reduced pressure to remove the solvent, and dichloromethane (400 mL) was added. The sample was washed three times with deionized water (80 mL * 3), separated, mixed with silica gel, and dry-coated onto a column for silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 20:1 as eluent). After elution, the sample was concentrated under reduced pressure at 60°C for 1 hour to obtain compound A6-3 (42.09 g, purity: 99.12%, yield: 79.81%), mass spectrometry: 282.03 (M+H).

[0127] Synthesis of compound A6-5 Compound A6-3 (42.00 g, 149.11 mmol), compound A6-4 (48.09 g, 164.02 mmol, CAS: 1219637-88-3), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (1.09 g, 1.49 mmol), potassium carbonate (51.52 g, 372.78 mmol), 1,4-dioxane (500 mL), and deionized water (100 mL) were added to a 1000 mL three-necked round-bottom flask. The flask was purged with nitrogen three times. The system was then heated to 80 °C and reacted for 4 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 10:1 as the developing solvent). Compound A6-3 was completely consumed.

[0128] The sample was cooled to 60°C, concentrated under reduced pressure to remove the solvent, and dichloromethane (400 mL) was added. The sample was washed three times with deionized water (80 mL * 3), separated, mixed with silica gel, and dry-coated onto a column for silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 15:1 as eluent). After elution, the sample was concentrated under reduced pressure at 60°C for 1 hour to obtain compound A6-5 (44.16 g, purity: 99.25%, yield: 71.81%), mass spectrometry: 413.12 (M+H).

[0129] Synthesis of compound A6-6 Compound A6-5 (44.00 g, 106.69 mmol), cesium carbonate (69.52 g, 213.37 mmol), and N,N-dimethylacetamide (500 mL) were added to a 1000 mL three-necked round-bottom flask. The mixture was purged with nitrogen three times, and then the system was heated to 120 °C and reacted for 4 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 5:1 as the developing solvent). Compound A6-5 was completely consumed.

[0130] Cool to 60℃, add dichloromethane (400mL), wash three times with deionized water (150mL*3), separate the contents, mix with silica gel, dry-load the sample onto a column, and perform silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 10:1 as eluent). After elution, concentrate under reduced pressure at 60℃ for 1 hour to obtain compound A6-6 (29.42g, purity: 99.30%, yield: 70.27%), mass spectrometry: 393.12 (M+H).

[0131] Synthesis of compound A6-7 Compound A6-6 (41.00 g, 104.48 mmol), triphenylphosphine (54.81 g, 208.96 mmol), and o-dichlorobenzene (500 mL) were added to a 1000 mL three-necked round-bottom flask. The mixture was purged with nitrogen three times, and then the system was heated to 200 °C and reacted for 24 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 10:1 as the developing solvent). Compound A6-6 was completely consumed.

[0132] Cool to 60℃, add dichloromethane (200mL), wash three times with deionized water (150mL*3), separate the contents, mix with silica gel, dry-load the sample onto a column, and perform silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 10:1 as eluent). After elution, concentrate under reduced pressure at 60℃ for 1 hour to obtain compound A6-7 (26.71g, purity: 99.41%, yield: 70.93%), mass spectrometry: 361.13 (M+H).

[0133] Synthesis of compound A6-9 Compound A6-7 (26.00 g, 72.14 mmol), compound A6-8 (30.89 g, 144.28 mmol), tris(dibenzylacetone)palladium (1.32 g, 1.44 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (1.38 g, 2.89 mmol), cesium carbonate (58.76 g, 180.35 mmol), and toluene (400 mL) were added to a 1000 mL three-necked round-bottom flask. The mixture was purged with nitrogen three times, and then the system was heated to 90 °C and reacted for 4 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 10:1 as the developing solvent). Compound A6-7 was completely consumed.

[0134] The sample was cooled to 60°C, concentrated under reduced pressure to remove some of the solvent, and dichloromethane (300 mL) was added. The sample was washed three times with deionized water (80 mL * 3), separated, mixed with silica gel, and dry-coated onto a column for silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 10:1 as eluent). After elution, the sample was concentrated under reduced pressure at 60°C for 1 hour to obtain compound A6-9 (24.77 g, purity: 99.25%, yield: 69.56%), mass spectrometry: 494.22 (M+H).

[0135] Synthesis of compound A6-10 Compound A6-9 (24.00 g, 48.62 mmol) and dichloromethane (250 mL) were added to a 500 mL three-necked round-bottom flask. The flask was purged with nitrogen three times. The system was then cooled to 0 °C and stirred for 10 min. A solution of boron tribromide (24.36 g, 97.24 mmol) in dichloromethane was then slowly added dropwise over 10 min. After the addition was complete, the mixture was stirred at 0 °C for 4 hours. The reaction was monitored by TLC (using hexane:tetrahydrofuran = 5:1 as the developing solvent). Compound A6-9 was completely consumed.

[0136] The mixture was heated to room temperature, and a large amount of water was added dropwise with stirring to quench the remaining boron tribromide. The mixture was separated, mixed with silica gel, and then dry-coated onto a column for silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:tetrahydrofuran = 5:1 as eluent). After elution, the mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain compound A6-10 (17.16 g, purity: 99.39%, yield: 73.59%), mass spectrometry: 480.20 (M+H).

[0137] Synthesis of compound A6-12 Compound A6-10 (17.00 g, 35.45 mmol), compound A6-11 (18.29 g, 106.34 mmol), cuprous iodide (6.75 g, 35.45 mmol), 2-pyridinecarboxylic acid (4.36 g, 35.45 mmol), potassium phosphate (22.57 g, 106.34 mmol), and dimethyl sulfoxide (350 mL) were added to a 500 mL three-necked round-bottom flask. The flask was purged with nitrogen three times, and then the system was heated to 150 °C and reacted for 10 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 10:1 as the developing solvent). Compound A6-10 was completely consumed.

[0138] Cool to 60℃, add dichloromethane (300mL), wash three times with deionized water (150mL*3), separate the contents, mix with silica gel, dry-load the sample onto a column, and perform silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 10:1 as eluent). After elution, concentrate under reduced pressure at 60℃ for 1 hour to obtain compound A6-12 (15.82g, purity: 99.20%, yield: 78.20%), mass spectrometry: 571.24 (M+H).

[0139] Synthesis of compound A6-14 Compound A6-12 (15.50 g, 227.16 mmol), compound A6-13 (11.74 g, 32.59 mmol, CAS: 909114-39-2), tris(dibenzylacetone)palladium (1.24 g, 1.36 mmol), 1,1'-binaphthyl-2,2'-bis(diphenylphosphine) (1.69 g, 92.72 mmol), sodium tert-butoxide (6.53 g, 67.90 mmol), and toluene (350 mL) were added to a 500 mL three-necked round-bottom flask. The flask was purged with nitrogen three times, and then the system was heated to 110 °C and reacted for 24 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 10:1 as the developing solvent). Compound A6-12 was completely consumed.

[0140] The solution was cooled to 60°C, concentrated under reduced pressure to remove some of the solvent, and dichloromethane (300 mL) was added. The solution was washed three times with deionized water (80 mL * 3), separated, mixed with silica gel, and dry-coated onto a column for silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 10:1 as eluent). After elution, the solution was concentrated under reduced pressure at 60°C for 1 hour to obtain compound A6-14 (15.52 g, purity: 99.34%, yield: 67.22%), mass spectrometry: 850.44 (M+H).

[0141] Synthesis of compound A6-15 Compound A6-14 (15.00 g, 17.64 mmol), ammonium hexafluorophosphate (8.63 g, 52.93 mmol), and triethyl orthoformate (200 mL) were added to a 500 mL three-necked round-bottom flask. The mixture was purged with nitrogen three times, and then the system was heated to 75 °C and reacted for 9 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 5:1 as the developing solvent). Compound A6-14 was completely consumed.

[0142] The mixture was cooled to 60℃, and saturated ammonium chloride aqueous solution (50 mL * 3) was added. The mixture was stirred at room temperature for 30 min, extracted with ethyl acetate (100 mL * 3), separated, mixed with silica gel, and dry-coated onto a silica gel column for purification (200-300 mesh silica gel, dichloromethane as eluent). A black substance was obtained, which was then hot-beaten with n-hexane (100 mL) at 60℃ for 4 h, followed by sonication for 30 min. The mixture was filtered to obtain the solid compound A6-15 (13.24 g, purity: 99.22%, yield: 74.58%), mass spectrometry: 1006.40 (M+H).

[0143] Synthesis of compound A6 Compound A6-15 (13.00 g, 12.92 mmol), (1,5-cyclooctadiene)diplatinum(II) chloride (5.80 g, 15.51 mmol), sodium acetate (3.18 g, 38.76 mmol), and diethylene glycol dimethyl ether (200 mL) were added to a 500 mL three-necked round-bottom flask. The flask was purged with nitrogen three times, and then the system was heated to 140 °C and reacted for 26 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 5:1 as the developing solvent). Compound A6-15 was completely consumed.

[0144] The solution was cooled to 60°C, and 200 mL of dichloromethane was added. The sample was washed three times with deionized water (150 mL x 3). The mixture was separated, mixed with silica gel, and dry-coated onto a silica gel column for purification (200-300 mesh silica gel, hexane:dichloromethane = 5:1 as eluent). After elution, the solution was concentrated under reduced pressure at 60°C for 1 hour to obtain a solid compound. The solid was recrystallized from dichloromethane:methanol = 2:1 to obtain compound A6 (5.34 g, purity: 99.88%, yield: 39.20%). The 5.34 g crude compound A6 was then purified by sublimation to obtain sublimed pure compound A6 (2.01 g, purity: 99.90%, yield: 37.64%), mass spectrometry: 1054.38 (M+H).

[0145] 1H NMR (400 MHz, CDCl3) δ 8.72(d, J = 7.8 Hz, 1H), 8.23 ​​– 8.18 (m,2H), 7.85 (dd, J = 7.2, 1.2 Hz, 1H), 7.78 – 7.67 (m, 4H), 7.57 – 7.52 (m,2H), 7.40 – 7.26 (m, 3H), 7.24 – 7.18 (m, 3H), 7.13 – 7.08 (m, 2H), 7.04 –6.99 (m, 1H), 6.92 (d, J = 2.2 Hz, 2H), 6.85 (dd, J = 7.3, 1.3 Hz, 1H), 6.74(s, 1H), 6.45 (dd, J = 7.8, 1.2 Hz, 1H), 5.60 (s, 1H), 1.35 (d, J = 0.8 Hz, 27H). Synthesis of intermediate compound A35-3

[0146] Synthesis of compound A35-2 Following the synthesis and purification method of compound A6-9, only the corresponding raw materials need to be changed to obtain the target compound A35-2 (15.20 g, purity: 99.36%, yield: 69.22%), mass spectrometry: 528.20 (M+H). Compound A35-1 has the CAS number 1438809-78-9.

[0147] Synthesis of compound A35-3 Following the synthesis and purification method of compound A6-10, only the corresponding raw materials need to be changed to obtain the target compound A35-3 (10.72g, purity: 99.56%, yield: 73.42%), mass spectrometry: 514.18 (M+H).

[0148] Synthesis of intermediate compound A43-3

[0149] Synthesis of compound A43-3 Compound A43-1 (15.00 g, 62.91 mmol), compound A43-2 (13.39 g, 52.42 mmol, CAS: 2725027-17-6), tris(dibenzylacetone)palladium (0.47 g, 0.62 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.47 g, 1.24 mmol), cesium carbonate (42.70 g, 131.05 mmol), and 1,4-dioxane (200 mL) were added to a 500 mL three-necked round-bottom flask. The flask was purged with nitrogen three times, and then the system was heated to 90 °C and reacted for 4 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 15:1 as the developing solvent). Compound A43-2 was completely consumed.

[0150] The solution was cooled to 60°C, concentrated under reduced pressure to remove some of the solvent, and dichloromethane (200 mL) was added. The solution was washed three times with deionized water (80 mL * 3), separated, mixed with silica gel, and dry-coated onto a column for silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 10:1 as eluent). After elution, the solution was concentrated under reduced pressure at 60°C for 1 hour to obtain compound A43-3 (15.17 g, purity: 99.47%, yield: 79.08%), mass spectrometry: 366.18 (M+H).

[0151] Synthesis of intermediate compound A61-6

[0152] Synthesis of compound A61-2 Following the synthesis and purification method of compound A6-5, only the corresponding raw materials need to be changed to obtain the target compound A61-2 (37.52 g, purity: 99.15%, yield: 76.17%), mass spectrometry: 463.14 (M+H). Compound A61-1 has the CAS number 2259354-30-6.

[0153] Synthesis of compound A61-3 Following the synthesis and purification method of compound A6-6, only the corresponding raw materials need to be changed to obtain the target compound A61-3 (25.94g, purity: 99.30%, yield: 73.28%), mass spectrometry: 443.13 (M+H).

[0154] Synthesis of compound A61-4 Following the synthesis and purification method of compound A6-7, only the corresponding raw materials need to be changed to obtain the target compound A61-4 (17.02g, purity: 99.27%, yield: 71.95%), mass spectrometry: 411.14 (M+H).

[0155] Synthesis of compound A61-5 Following the synthesis and purification method of compound A6-9, only the corresponding raw materials need to be changed to obtain the target compound A61-5 (16.28 g, purity: 99.41%, yield: 72.30%), mass spectrometry: 544.23 (M+H).

[0156] Synthesis of compound A61-6 Following the synthesis and purification method of compound A6-10, only the corresponding raw materials need to be changed to obtain the target compound A61-6 (12.15g, purity: 99.55%, yield: 77.95%), mass spectrometry: 530.22 (M+H).

[0157] Synthesis of intermediate compounds A111-6 and A111-9

[0158] Synthesis of compound A111-2 Following the synthesis and purification method of compound A6-5, only the corresponding raw materials need to be changed to obtain the target compound A111-2 (39.21 g, purity: 99.13%, yield: 79.60%), mass spectrometry: 463.14 (M+H). Compound A111-1 has the CAS number 2794149-79-2.

[0159] Synthesis of compound A111-3 Following the synthesis and purification method of compound A6-6, only the corresponding raw materials need to be changed to obtain the target compound A111-3 (28.46 g, purity: 99.29%, yield: 76.27%), mass spectrometry: 443.13 (M+H).

[0160] Synthesis of compound A111-4 Following the synthesis and purification method of compound A6-7, only the corresponding raw materials need to be changed to obtain the target compound A111-4 (18.56g, purity: 99.22%, yield: 68.03%), mass spectrometry: 411.14 (M+H).

[0161] Synthesis of compound A111-5 Following the synthesis and purification method of compound A6-9, only the corresponding raw materials need to be changed to obtain the target compound A111-5 (16.22g, purity: 99.39%, yield: 68.03%), mass spectrometry: 544.23 (M+H).

[0162] Synthesis of compound A111-6 Following the synthesis and purification method of compound A6-10, only the corresponding raw materials need to be changed to obtain the target compound A111-6 (12.12 g, purity: 99.54%, yield: 77.76%), mass spectrometry: 530.22 (M+H).

[0163] Synthesis of compound A111-9 Compound A111-7 (10.00 g, 66.67 mmol), compound A111-8 (19.86 g, 66.67 mmol), tetrakis(triphenylphosphine)palladium (0.77 g, 0.67 mmol), potassium carbonate (23.04 g, 166.68 mmol), 1,4-dioxane (200 mL), and deionized water (50 mL) were added to a 500 mL three-necked round-bottom flask. The flask was purged with nitrogen three times. The system was then heated to 50 °C and reacted for 4 hours. The reaction was monitored by TLC (using n-hexane:ethyl acetate = 15:1 as the developing solvent). Compound A111-8 was completely consumed.

[0164] The solution was cooled to 60°C, concentrated under reduced pressure to remove some of the solvent, and dichloromethane (200 mL) was added. The solution was washed three times with deionized water (80 mL * 3), separated, mixed with silica gel, and dry-coated onto a column for silica gel column chromatography purification (200-300 mesh silica gel, n-hexane:ethyl acetate = 15:1 as eluent). After elution, the solution was concentrated under reduced pressure at 60°C for 1 hour to obtain compound A111-9 (14.21 g, purity: 99.32%, yield: 77.17%), mass spectrometry: 276.03 (M+H).

[0165] Synthesis of intermediate compounds A154-8 and A154-11

[0166] Synthesis of compound A154-3 Following the synthesis and purification method of compound A6-3, only the corresponding raw materials need to be changed to obtain the target compound A154-3 (33.17g, purity: 99.35%, yield: 73.17%), mass spectrometry: 282.03 (M+H).

[0167] Synthesis of compound A154-4 Following the synthesis and purification method of compound A6-5, only the corresponding raw materials need to be changed to obtain the target compound A154-4 (34.20 g, purity: 99.19%, yield: 70.78%), mass spectrometry: 413.12 (M+H).

[0168] Synthesis of compound A154-5 Following the synthesis and purification method of compound A6-6, only the corresponding raw materials need to be changed to obtain the target compound A154-5 (22.19 g, purity: 99.24%, yield: 68.59%), mass spectrometry: 393.12 (M+H).

[0169] Synthesis of compound A154-6 Following the synthesis and purification method of compound A6-7, only the corresponding raw materials need to be changed to obtain the target compound A154-6 (14.25g, purity: 99.31%, yield: 70.52%), mass spectrometry: 361.13 (M+H).

[0170] Synthesis of compound A154-7 Following the synthesis and purification method of compound A6-9, only the corresponding raw materials need to be changed to obtain the target compound A154-7 (14.14 g, purity: 99.36%, yield: 73.75%), mass spectrometry: 494.22 (M+H).

[0171] Synthesis of compound A154-8 Following the synthesis and purification method of compound A6-10, only the corresponding raw materials need to be changed to obtain the target compound A154-8 (10.68g, purity: 99.52%, yield: 78.52%), mass spectrometry: 480.20 (M+H).

[0172] Synthesis of compound A154-11 Following the synthesis and purification method of compound A43-3, only the corresponding raw materials need to be changed to obtain the target compound A154-11 (10.59 g, purity: 99.44%, yield: 80.02%), mass spectrometry: 317.17 (M+H).

[0173] Synthesis of intermediate compound A161-5

[0174] Synthesis of compound A161-1 Following the synthesis and purification method of compound A6-5, only the corresponding raw materials need to be changed to obtain the target compound.

[0175] A161-1 (36.90 g, purity: 99.27%, yield: 74.91%), mass spectrometry: 463.14 (M+H).

[0176] Synthesis of compound A161-2 Following the synthesis and purification method of compound A6-6, only the corresponding raw materials need to be changed to obtain the target compound A161-2 (24.98g, purity: 99.16%, yield: 72.53%), mass spectrometry: 443.13 (M+H).

[0177] Synthesis of compound A161-3 Following the synthesis and purification method of compound A6-7, only the corresponding raw materials need to be changed to obtain the target compound A161-3 (16.12g, purity: 99.20%, yield: 70.92%), mass spectrometry: 411.14 (M+H).

[0178] Synthesis of compound A161-4 Following the synthesis and purification method of compound A6-9, only the corresponding raw materials need to be changed to obtain the target compound A161-4 (14.80 g, purity: 99.42%, yield: 69.84%), mass spectrometry: 544.23 (M+H).

[0179] Synthesis of compound A161-5 Following the synthesis and purification method of compound A6-10, only the corresponding raw materials need to be changed to obtain the target compound A161-5 (11.39 g, purity: 99.50%, yield: 80.63%), mass spectrometry: 530.22 (M+H).

[0180] Combining the above intermediates, compounds A18, A35, A43, A61, A111, A123, A154, and A161 were prepared using a similar synthetic method to compound A6, the difference being the different raw materials used, as shown in Table 1 below.

[0181] Table 1

[0182] Application example: Fabrication of light-emitting devices As attached Figure 2 As shown, the light-emitting device includes a glass substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4 (HTL1), a second hole transport layer 5 (HTL2), a light-emitting layer 6, a hole blocking layer 7 (HBL), an electron transport layer 8 (ETL), and a cathode 9, which are stacked together.

[0183] A glass substrate 1 with ITO (100nm) transparent electrodes (anode 2 and cathode 9) measuring 50mm*50mm*1.0mm was ultrasonically cleaned in ethanol for 10 minutes, dried at 150 degrees Celsius, and then treated with N2Plasma for 30 minutes. The washed glass substrate is mounted on the substrate support of the vacuum evaporation apparatus. First, HATCN compound is deposited on the side with transparent electrode lines in a manner that covers the transparent electrode to form a thin film (hole injection layer 3) with a thickness of 5 nm. Then, an HTM1 layer is deposited to form a thin film with a thickness of 60 nm as HTL1 (first hole transport layer 4). Next, an HTM2 layer is deposited on the HTM1 film to form a thin film with a thickness of 10 nm as HTL2 (second hole transport layer 5). Then, host material 1, host material 2 and guest material (host material 1: host material 2: guest material weight ratio: 47.5%: 47.5%: 5%) are deposited on the HTM2 film using a co-evaporation mode to form a light-emitting layer 6 with a thickness of 25 nm. A hole blocking layer 7 (HBL) with a thickness of 5 nm and an electron transport layer 8 with a thickness of 350 nm are sequentially formed on the light-emitting layer by vapor deposition. The guest material in the light-emitting layer is the tetradentate platinum complex of this application or the comparative compounds 1-3. Then, Mg / Ag (100 nm, 1:9) is deposited as the cathode material by co-evaporation.

[0184] The structural formulas of HAT-CN, HTL, EBL, host material 1, host material 2, HBL, ETL, LiQ, and comparative compounds 1-3 are as follows:

[0185] evaluate: The above-mentioned light-emitting devices were subjected to device performance testing. The tetradentate platinum complex prepared in this application and comparative compounds 1-3 were used as guest materials in the light-emitting layer for comparison. A constant current power supply (Keithley 2400) was used, with a fixed current density flowing through the light-emitting element, and the emission spectrum was measured using a spectroradiometer (CS 2000). Simultaneously, at 10 mA / cm²... 2 The IVL (current-voltage-luminance) performance of the devices was measured, and the lifetime of the LT95 devices was tested at 5000 nits. The results are shown in Table 2 below (the examples in Table 2 use the tetradentate platinum complex of this application, and the comparative examples use comparative compounds).

[0186] Table 2

[0187] As can be seen from the data comparison in the table above, when the compounds of this application are used as guest materials for orange and red light in light-emitting devices, they exhibit superior performance in terms of driving voltage, luminous efficiency, and device lifetime compared to comparative compounds 1-3.

[0188] The above results indicate that the compounds of this application possess advantages such as good optical, electrical, and thermal stability, high luminous efficiency, low voltage, and long lifetime, making them suitable for use in organic light-emitting devices. In particular, as orange and red light-emitting materials, they have the potential for application in the light-emitting device industry.

[0189] The embodiments of this application have been described in detail above, but this application is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of this application.

Claims

1. A tetradentate platinum complex, characterized in that: The general structural formula of the tetradentate platinum complex is shown in one of the following formulas: Equation (1) Equation (2) Among them, ring A, ring B, ring C and ring D are independently selected from substituted or unsubstituted benzene rings or substituted or unsubstituted naphthalene rings; X1to X4are independently selected from N or CR a ; R a Selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboron, C6-C60 arylboron, C6-C60 arylphosphine, C6-C60 arylamino, or substituted or unsubstituted C6-C60 aryl, with two adjacent R a They can be connected to form a parallel loop; R1, R2, and R3 are each independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphinyl, C6-C60 arylamino, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C1-C40 alkyl. a and b represent integers from 0 to 4; c represents integers from 0 to 3; Ar1 is selected from substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C3-C60 heteroaryl; The substitutions in ring A, ring B, ring C, and ring D are each independently represented by at least one of deuterium, halogen, cyano, isocyano, phosphinyl, halo-C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amino, deuterium-substituted or unsubstituted C1-C10 alkyl, C1-C6 alkyl-substituted or unsubstituted C6-C30 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C30 heteroaryl, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions; The substitution in Ar1 means that it is substituted by at least one of deuterium, halogen, cyano, isocyano, phosphin, halo-C1-C6 alkyl, C3-C16 cycloalkyl, deuterium-substituted or unsubstituted C1-C10 alkyl or C1-C6 alkyl-substituted amino group, and the number of substitutions is from monosubstituted to the maximum number of substitutions. The R a The substitutions in R1, R2 and R3 independently represent substitution by at least one of deuterium, halogen, cyano, isocyano, phosphin, halo-C1-C6 alkyl, C3-C16 cycloalkyl, deuterium-substituted or unsubstituted C1-C10 alkyl or C1-C6 alkyl-substituted amino groups, with the number of substitutions ranging from monosubstituted to the maximum number of substitutions; The heteroatoms in the heteroalkyl, heterocycloalkyl, and heteroaryl groups are each independently selected from at least one of O, S, N, P, B, Si, Ge, or Se.

2. The tetradentate platinum complex according to claim 1, characterized in that: The structural formula of the tetradentate platinum complex is selected from one of the following general formulas: Among them, Y1~Y9 and Z1~Z9 are each independently CR b ; R b Each is independently selected from at least one of hydrogen, deuterium, halogen, cyano, isocyano, phosphinyl, halogenated C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amino, deuterated or unsubstituted C1-C6 alkyl, C1-C6 alkyl-substituted or unsubstituted C6-C30 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C30 heteroaryl.

3. The tetradentate platinum complex according to claim 1, characterized in that: The tetradentate platinum complex contains at least one deuterium atom; and / or, the substitutions in ring A, ring B, ring C, and ring D independently represent substitution by at least one of deuterium, halogen, cyano, isocyano, phosphinyl, deuterium-substituted or unsubstituted C1-C6 alkyl, halo-C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl-substituted amino, C1-C6 alkyl-substituted or unsubstituted C6-C20 aryl, or C1-C6 alkyl-substituted or unsubstituted C3-C20 heteroaryl, with the substitution number ranging from monosubstituted to the maximum number of substitutions; the substitution in Ar1 represents substitution by at least one of deuterium, cyano, isocyano, halo-C1-C6 alkyl, C3-C8 cycloalkyl, or C1-C6 alkyl-substituted amino, with the substitution number ranging from monosubstituted to the maximum number of substitutions.

4. The tetradentate platinum complex according to claim 1 or 2, characterized in that: The Ar1 is selected from substituted or unsubstituted methyl, substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraxyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted pyreneyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted fluoranyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, or combinations thereof.

5. The tetradentate platinum complex according to claim 1 or 2, characterized in that: R a Selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphinyl, C6-C30 arylamino, or substituted or unsubstituted C6-C30 aryl, with two adjacent R a They can be connected to form a parallel loop; And / or, R1, R2 and R3 are each independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C5-C40 heteroaryl, C1-C20 alkoxy, C6-C20 aryloxy, substituted or unsubstituted C6-C40 aryl or substituted or unsubstituted C1-C20 alkyl.

6. The tetradentate platinum complex according to claim 1 or 2, characterized in that: At least one of X1 to X4 is N and / or R. a The substitutions in the aryl groups of R1, R2, or R3 are each independently selected from at least one of deuterium, cyano, halogen, deuterated C1-C6 alkyl, halo-C1-C6 alkyl, or C1-C6 alkyl; the substitutions in the alkyl groups of R1, R2, or R3 are each independently selected from at least one of deuterium, cyano, halogen, deuterated C1-C6 alkyl, halo-C1-C6 alkyl, or C1-C6 alkyl.

7. The tetradentate platinum complex according to claim 1, characterized in that: The general structural formula of the tetradentate platinum complex is selected from formula (1), wherein ring A and ring B are independently selected from substituted or unsubstituted benzene rings or substituted or unsubstituted naphthalene rings, Ar1 is selected from C1-C10 alkyl substituted or unsubstituted C6-C30 aryl groups; X1~X4 are all CH; R2 is selected from C1-C10 alkyl groups; a and c represent 0, and b represents an integer from 0 to 2; wherein the substitution in ring A and ring B is independently represented by at least one of deuterium, halogen, cyano, isocyano, phosphin or C1-C10 alkyl groups, and the number of substitutions is from monosubstituted to the maximum number of substitutions.

8. The tetradentate platinum complex according to claim 1 or 2, characterized in that: The compound is one of the following structural formulas, or a structure in which hydrogen is partially or completely substituted by deuterium or fluorine: 。 9. A light-emitting device, characterized in that: It includes a cathode and an anode, with an organic layer between the cathode and the anode, the organic layer comprising the tetradentate platinum complex as described in any one of claims 1 to 8.

10. The light-emitting device according to claim 9, characterized in that: The organic layer includes a light-emitting layer, which contains the tetradentate platinum complex.

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