An arylamine compound and a device thereof

Abstract

The application belongs to the technical field of organic synthesis, and particularly relates to an arylamine compound and a device thereof. The application introduces an arylamine group with a three-dimensional structure into a five-membered heterocycle containing three heteroatoms with a high triplet energy level after fusing the five-membered heterocycle with a phenanthrene ring, and constructs a new type of arylamine compound. Through the synergy of the phenanthrene-fused five-membered heterocycle with high skeleton stability and high triplet energy level and the arylamine group with twisted configuration and increased intermolecular steric hindrance, precise molecular optimization of existing materials is realized, which has important value in an organic electroluminescent device.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to an aromatic amine compound and its device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have become the core of next-generation display and lighting technologies due to their advantages such as self-illumination, wide color gamut, high contrast, low power consumption, and flexible display capabilities. Among these, the light-emitting materials and carrier transport materials are the key factors determining the performance of OLED devices.

[0003] In recent years, polycyclic aromatic hydrocarbon systems containing nitrogen, sulfur, and other heteroatoms have attracted much attention due to their rigid planar structure and tunable electronic properties. Chinese patent (publication number CN112979558A) describes a red-light host material (compound H1-51) with a phenanthreneoxazole structural unit linked to a diarylamine. Its ultraviolet-visible absorption spectrum (UV) is 406 nm, and its photoluminescence (PL) is 427 nm. As an energy donor, the emission spectrum of the host material needs to overlap as much as possible with the absorption spectrum of the guest material. Only then can the host material efficiently transfer excited-state energy to the guest dye, which acts as the energy acceptor. The device performance of devices using this type of material as a host material needs further improvement. Chinese patent (publication number CN116874477A) discloses the application of compounds containing heteroatoms as capping materials in organic electroluminescent devices (compounds 34, 109, etc.). These heteroatom-containing compounds exhibit good refractive index and good absorption in the ultraviolet band, revealing the application potential of compounds containing phenanthrene-oxadiazole and phenanthrene-thiadiazole structural units linked to diarylamines in capping layers. However, existing materials of this type still have the following shortcomings: Firstly, phenanthrene-oxadiazole has limited electron transport capability; even after being linked to aromatic amines, its electron mobility is generally lower than its hole mobility, causing the carrier recombination region to deviate from the center of the luminescent layer. Secondly, academia and industry have long faced the dilemma of achieving a balance between high color purity, high efficiency, and long lifetime. Under this new paradigm, the requirements for the host material itself have become more stringent and specific, aiming to achieve stable, efficient, and high-color-purity luminescence.

[0004] Therefore, how to achieve a high balance between electron and hole transport while maintaining a wide bandgap and high thermal stability, optimize the energy level matching between the host material and adjacent functional layers, and achieve high color purity emission spectrum remains a technical challenge that urgently needs to be solved in the field of OLED materials. Summary of the Invention

[0005] To solve the above-mentioned technical problems, the present invention provides an aromatic amine compound, which is a compound represented by the following chemical formula 1: ; In the above chemical formula 1, X is one of O, S, and N (R1); Y is N; and R1 is C6~C. 12 The aryl group, wherein the aryl group is unsubstituted or substituted with a C1-C4 alkyl group; Ar1 ​​is the part shown in Formula 2 below: Chemical formula 2 .

[0006] In the above chemical formula 2, * represents the connection site between Ar1 and L1; L1, L2, and L3 may be the same or different from each other, and are independently single bonds or C6-C6 bonds. 18 The arylene group is unsubstituted or substituted with a C1-C4 alkyl group; Ar2 and Ar3 are the same or different from each other, and are independently C6-C4 respectively. 18 aryl, C6-C 24 Arylsilyl, C6~C 24 Aromatic amino groups or C6-C 12 The heteroaryl group, C6-C 18 aryl, C6-C 24 Arylsilyl, C6~C 24 Aromatic amino groups or C6-C 12 The heteroaryl groups are either unsubstituted or substituted with C1-C4 alkyl groups; R2 and R3 may be the same as or different from each other, and are independently C1-C4. 18 Alkyl or C6~C 12 The aryl group, C6~C 12 The aryl group is either unsubstituted or substituted with a C1-C4 alkyl group; m1 is 1 or 2; m2 and m3 are the same or different from each other, and are 0, 1 or 2 independently, respectively.

[0007] According to the above technical solution, C6~C 12 aryl, C6-C 18 aryl, C6-C 18 The aryl group is a group formed by 1-3 benzene ring groups linked by single bonds, alkyl groups, fused rings, or combinations thereof, and the group is not substituted or may be substituted by C1-C4 alkyl groups; the C6-C 24 The arylsilyl group is C6~C 12 A group formed by replacing three hydrogen atoms in a silyl group with any three of the aryl groups, and such group is not substituted or may be further substituted by C1-C4 alkyl groups; the C6-C 24 The aromatic amino group is C6~C 18 aryl, C6-C 12 A group formed by replacing two hydrogen atoms in an amino group with any two of the heteroaryl groups, and the group is not substituted or may be further substituted by C1-C4 alkyl groups; the C6-C 12The heteroaryl group is a group formed by connecting 1-2 benzene ring groups and a five-membered heterocyclic group through a fused ring, and the group is not substituted or can be further substituted by C1-C4 alkyl groups.

[0008] According to the above technical solution, C6~C 12 aryl, C6-C 18 aryl, C6-C 18 The aryl groups may be the same or different from each other, and are each independently one of a monocyclic aromatic hydrocarbon group, a biphenyl-type polycyclic aromatic hydrocarbon group, or a fused-ring polycyclic aromatic hydrocarbon group; the C6-C 12 The heteroaryl group is a fused-ring polycyclic aromatic hydrocarbon group containing one heteroatom of O, N, or S; the monocyclic aromatic hydrocarbon group, biphenyl-type polycyclic aromatic hydrocarbon group, fused-ring polycyclic aromatic hydrocarbon group, or fused-ring polycyclic aromatic hydrocarbon group is either unsubstituted or can be further substituted by C1-C4 alkyl groups.

[0009] According to the above technical solution, the monocyclic aromatic group is phenyl, which is unsubstituted or may be substituted by C1-C4 alkyl groups; the biphenyl-type polycyclic aromatic group is selected from biphenyl and terphenyl, which is unsubstituted or may be substituted by C1-C4 alkyl groups; the fused-ring aromatic group is selected from naphthyl, anthraceneyl, phenanthryl, fluoranyl, and fluorenyl, which is unsubstituted or may be substituted by C1-C4 alkyl groups; the fused-ring polycyclic aromatic heterocyclic group is selected from indolyl, benzofuranyl, benzothiopheneyl, benzimidazolyl, benzooxazolyl, benzothiazolyl, carbazoleyl, dibenzofuranyl, and dibenzothiopheneyl, which is unsubstituted or may be substituted by C1-C4 alkyl groups.

[0010] According to the above technical solution, R1 is a group formed by 1-2 benzene ring groups connected by single bonds or fused rings, which is not substituted or is further substituted by C1-C4 alkyl groups; as an example of R1, R1 is selected from phenyl, biphenyl, naphthyl, which is not substituted or can be substituted by C1-C4 alkyl groups.

[0011] According to the above technical solution, L1, L2, and L3 may be the same or different from each other, and are groups formed by 1-3 benzene ring groups connected by single bonds, fused rings, or combinations thereof, which are unsubstituted or may be substituted by C1-C4 alkyl groups; as examples of L1, L2, and L3, L1, L2, and L3 may be independently phenyl, biphenyl, terphenyl, or naphthyl, which are unsubstituted or may be substituted by C1-C4 alkyl groups.

[0012] According to the above technical solution, when Ar2 and Ar3 are C6 to C6... 18When Ar2 and Ar3 are aryl groups, they are aryl groups formed by 1-3 benzene ring groups linked by single bonds, alkyl groups, fused rings, or combinations thereof, and are unsubstituted or may be substituted by C1-C4 alkyl groups. Examples of Ar2 and Ar3 include Ar2 and Ar3 being independently phenyl, biphenyl, terphenyl, naphthyl, anthraceneyl, phenanthryl, fluorenyl, or fluorenyl groups, respectively, unsubstituted or may be substituted by C1-C4 alkyl groups. When Ar2 and Ar3 are C6-C6... 24 When Ar2 and Ar3 are arylsilyl groups, Ar2 and Ar3 are independently triphenylsilyl, tetraphenylsilyl, and biphenyldiphenylsilyl, respectively. When Ar2 and Ar3 are C6 to C6... 24 When Ar2 and Ar3 are aromatic amino groups, they are groups formed by replacing two hydrogen atoms in the amino group with any two of the following: monocyclic aromatic groups, biphenyl-type polycyclic aromatic groups, fused-ring aromatic groups, and fused-ring polycyclic aromatic heterocyclic groups. The definitions of monocyclic aromatic groups, biphenyl-type polycyclic aromatic groups, fused-ring aromatic groups, and fused-ring polycyclic aromatic heterocyclic groups are the same as those described above. As examples of Ar2 and Ar3, Ar2 and Ar3 can be independently diphenylamino, diphenylamino, dinaphthylamino, terphenylaniline, biphenylaniline, naphthylaniline, dibenzofuranylaniline, dibenzothiopheneylaniline, carbazoleylphenylaniline, 9-phenylcarbazoleylaniline, and fluorenylaniline, which are unsubstituted or can be further substituted by C1-C4 alkyl groups. When Ar2 and Ar3 are C6-C4... 12 When Ar2 is a heteroaryl group, it is a group formed by connecting 1-2 benzene ring groups with a five-membered heterocyclic group containing one heteroatom of O, N, or S through a fused ring, which is unsubstituted or may be substituted by C1-C4 alkyl groups; as examples of Ar2 and Ar3, Ar2 and Ar3 can be independently indole, benzofuran, benzothiophene, benzoimidazolyl, benzooxazolyl, benzothiazolyl, carbazole, dibenzofuran, and dibenzothiophene, which are unsubstituted or may be substituted by C1-C4 alkyl groups.

[0013] According to the above technical solution, R2 and R3 may be the same or different from each other, and are independently C1-C4 alkyl groups and C6-C4 alkyl groups, respectively. 10 Cycloalkane group or C6~C 12 aryl groups, wherein C6~C 12 The aryl group is not substituted or may be further substituted by C1-C4 alkyl groups.

[0014] According to the above technical solution, the C1-C4 alkyl groups are selected from one of methyl, ethyl, and tert-butyl; the C6-C 10 The cycloalkane group is selected from cyclohexyl or adamantyl; the C6~C 12The aryl group is selected from one of phenyl, biphenyl, and naphthyl, and it is either unsubstituted or can be substituted by C1-C4 alkyl groups.

[0015] As a preferred technical solution, when R2 and R3 are C6-C 10 Cycloalkane group or C6~C 12 When R2 and R3 are aryl groups, m2 and m3 may be the same or different from each other, and are 0 or 1 independently, and m2 + m3 ≥ 1; m2 and / or m3 are 2 if and only if R2 and R3 are C1-C4 alkyl groups.

[0016] As a preferred technical solution, at least one of R2 and R3 is C6-C. 10 Cycloalkane group.

[0017] According to the above technical solution, the aromatic amine compound is selected from compounds represented by the following chemical formulas: 。

[0018] Another aspect of the present invention provides an organic electroluminescent device, comprising: a first electrode; a second electrode facing the first electrode; and a functional layer disposed between the first electrode and the second electrode; wherein the functional layer comprises an aromatic amine compound represented by the chemical formula 1.

[0019] According to the above technical solution, the functional layer includes one or more of a hole transport layer, a hole transport auxiliary layer, a light-emitting layer, an electron blocking layer, and an electron transport layer, and at least one of the light-emitting layer, hole transport layer, and hole transport auxiliary layer includes an aromatic amine compound represented by the chemical formula 1.

[0020] Furthermore, the light-emitting layer includes a light-emitting host and a dopant, wherein the light-emitting host includes an aromatic amine compound represented by the chemical formula 1.

[0021] This invention introduces a novel class of aromatic amine compounds by fusing a five-membered heterocycle containing three heteroatoms with a high triplet energy level to a phenanthrene ring, thereby creating an aromatic amine with a three-dimensional structure. In this class of aromatic amine compounds, on the one hand, the phenanthrene-containing five-membered heterocycle with three heteroatoms exhibits a stronger electron-withdrawing effect, and its intramolecular charge transfer (ICT) characteristics lead to a significant redshift in the emission spectrum, enabling it to more efficiently transfer excited-state energy to guest dyes, which act as energy acceptors. On the other hand, the fusion of the five-membered heterocycle with a high triplet energy level and the phenanthrene-containing ring ensures both skeletal stability and maintains a high T1 energy level. This, in conjunction with the stereoconfigured aromatic amine, significantly increases the steric hindrance between molecules. This molecular design addresses the traditional material dilemma of balancing stability and efficient energy transfer, endowing devices with advantages such as high luminous efficiency, low driving voltage, and high color purity, meeting the needs of AMOLED displays and high-end lighting applications. Attached Figure Description

[0022] Figure 1 The image shows the electroluminescence spectrum of the device prepared from compound 160. Detailed Implementation

[0023] The present invention will be further described below with reference to synthetic and device embodiments. The following embodiments will help to further understand the present invention. The embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention.

[0024] Unless otherwise specified, the test methods used in the embodiments are conventional methods; unless otherwise specified, the materials and reagents used are commercially available.

[0025] Synthesis Example 1: Synthesis of Intermediate 1-1 S1. Under nitrogen protection, 4-bromobenzoxadiazole (59.70 g, 300 mmol) and triisopropyl borate (84.63 g, 450 mmol) were added to 600 mL of tetrahydrofuran and stirred to dissolve. The reaction was cooled to -70 °C, and 2.5 M n-butyllithium (180 mL, 450 mmol) was slowly added dropwise. After the addition was complete, the reaction was continued at a controlled temperature for 1 h. 600 mL of 1 M dilute hydrochloric acid was added to the reaction solution and stirred. The upper organic phase was separated, and the lower aqueous phase was extracted with tetrahydrofuran and then combined with the upper organic phase. The mixture was concentrated, crystallized with petroleum ether, filtered, and dried to obtain 42.09 g of benzoxadiazole-4-ylboronic acid. S2. Under nitrogen protection, benzoxadiazole-4-ylboronic acid (32.79 g, 200 mmol), 2-bromo-4-chlorobenzaldehyde (46.09 g, 210 mmol), potassium carbonate (55.28 g, 400 mmol), and tetra(triphenylphosphine)palladium (1.16 g, 1 mmol) were added to 300 mL of a toluene / ethanol / water mixture with a volume ratio of 2:1:1. The mixture was stirred and mixed thoroughly, heated to 85 °C and reacted for 8 h. After cooling to room temperature, deionized water was added, and the mixture was filtered. The filtrate was separated, the organic phase was concentrated, and crystallized with ethanol along with the filter cake. After filtration and drying, 39.45 g of 2-(benzoxadiazole-4-yl)-4-chlorobenzaldehyde was obtained. S3. Under nitrogen protection, methoxymethyltriphenylphosphine chloride (64.28 g, 187.5 mmol) and potassium tert-butoxide (33.66 g, 300 mmol) were added to 400 mL of tetrahydrofuran. The mixture was cooled to 0 °C and stirred for 0.5 h. Then, 2-(benzoxadiazol-4-yl)-4-chlorobenzaldehyde (38.80 g, 150 mmol) was added and stirred at room temperature for 2 h. Deionized water was added and stirred. The mixture was separated into upper organic phase and the lower aqueous phase was extracted with ethyl acetate and then combined with the upper organic phase. The mixture was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. Methanol and / or petroleum ether were added to crystallize the filtrate. The crystals were filtered and dried to obtain 29.93 g of 2-(benzoxadiazol-4-yl)-4-chloro-1-(2-methoxyvinyl)benzene. S4. Under nitrogen protection, 2-(benzoxadiazol-4-yl)-4-chloro-1-(2-methoxyvinyl)benzene (28.67 g, 100 mmol) and nickel chloride (0.65 g, 60 mmol) were added to 200 mL of 1,2-dichloroethane. The mixture was stirred at room temperature for 2 hours. Deionized water was added, and the mixture was stirred. The upper organic phase was separated, and the lower aqueous phase was extracted with ethyl acetate. The aqueous phase was then combined with the upper organic phase, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The solution was then dissolved in toluene, cooled to room temperature to crystallize, filtered, and dried to obtain 19.38 g of intermediate 1-1. S5. Under nitrogen protection, intermediate 1-1 (15.28 g, 60 mmol) and triisopropyl borate (16.93 g, 90 mmol) were added to 150 mL of tetrahydrofuran and stirred to dissolve. The reaction was cooled to -70 °C, and 2.5 M n-butyllithium (36 mL, 90 mmol) was slowly added dropwise. After the addition was complete, the reaction was continued at a controlled temperature for 1 h. 120 mL of 1 M dilute hydrochloric acid was added to the reaction solution and stirred. The upper organic phase was separated, and the lower aqueous phase was extracted with tetrahydrofuran and then combined with the upper organic phase. The solution was concentrated, crystallized with ethanol, filtered, and then added to toluene for hot dissolution. After cooling to room temperature, ethanol was added to crystallize, filtered, and dried to obtain 13.07 g of intermediate 2-1.

[0026] MALDI-TOF-MS (m / z) measured value of product: 264.08; elemental analysis measured values ​​(%): C, 63.71; H, 3.43; N, 10.60.

[0027] Using raw material 1 from Table 1 instead of 4-bromobenzoxadiazole in Synthesis Example 1, and raw material 2 instead of 2-bromo-4-chlorobenzaldehyde in Synthesis Example 1, with the other raw materials and the same amount of substances added, the intermediates shown in Table 1 were obtained in the same manner as in Synthesis Example 1: Table 1 Synthesis Example 7: Synthesis of Compound 16 Under nitrogen protection, intermediate 1-6 (13.19 g, 40 mmol), bis(6-tert-butylbiphenyl-3-yl)amine (17.52 g, 40.4 mmol) (CAS: 3098484-33-1), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 16.63 g of compound 16, with a yield of 57.2%.

[0028] The measured value of the product by MALDI-TOF-MS (m / z) was 727.06.

[0029] Synthesis Example 8: Synthesis of Compound 33 Under nitrogen protection, intermediate 1-3 (10.83 g, 40 mmol), N-([1,1':4',1''-terphenyl]-4-yl)-[1,1':3',1''-terphenyl]-4'-amine (19.13 g, 40.4 mmol) (CAS: 2991054-04-5), sodium tert-butoxide (7.69 g, 80 mmol), and tris(dibenzylacetone)dipalladium (0.73 g) were disposed of. 0.8 mmol of tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) was added to 100 mL of toluene, stirred and heated to 115 °C for 16 h, cooled to room temperature, toluene and deionized water were added, stirred, separated, and the organic phase was dried with anhydrous magnesium sulfate, filtered, the filtrate was concentrated, dissolved in ethanol and heated to room temperature to crystallize, filtered, dried, and 16.73 g of compound 33 was obtained, with a yield of 59.1%.

[0030] The measured value of the product by MALDI-TOF-MS (m / z) was 707.84.

[0031] Synthesis Example 9: Synthesis of Compound 42 Under nitrogen protection, intermediate 1-3 (10.83 g, 40 mmol), N-(4'-(adamantane-1-yl)-[1,1'-biphenyl]-4-yl)-[1,1':3',1''-terphenyl]-4'-amine (21.48 g, 40.4 mmol) (CAS: 2759914-49-1), sodium tert-butoxide (7.69 g, 80 mmol), and tris(dibenzylacetone)dipalladium (0.7 g, 40 mmol) were reacted. 3 g (0.8 mmol) of tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) was added to 100 mL of toluene, stirred and heated to 115 °C for 16 h, cooled to room temperature, toluene and deionized water were added, stirred, separated, and the organic phase was dried with anhydrous magnesium sulfate, filtered, the filtrate was concentrated, dissolved in ethanol and heated to room temperature to crystallize, filtered, dried, and 17.43 g of compound 42 was obtained, with a yield of 56.9%.

[0032] The measured value of the product by MALDI-TOF-MS (m / z) was 765.51.

[0033] Synthesis Example 10: Synthesis of Compound 75 Under nitrogen protection, intermediate 1-3 (10.83 g, 40 mmol), N-([1,1'-biphenyl]-4-yl)-4'-(naphthyl-1-yl)-[1,1'-biphenyl]-4-amine (18.08 g, 40.4 mmol) (CAS: 897921-61-8), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 16.09 g of compound 75, with a yield of 59.0%.

[0034] The measured value of the product by MALDI-TOF-MS (m / z) was 681.82.

[0035] Synthesis Example 11: Synthesis of Compound 102 Under nitrogen protection, intermediate 1-2 (10.19 g, 40 mmol), N-(4-(phenanthrene-9-yl)phenyl)-[1,1'-biphenyl]-2-amine (17.03 g, 40.4 mmol) (CAS: 2425814-19-1), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 14.69 g of compound 102, with a yield of 57.4%.

[0036] The measured value of the product by MALDI-TOF-MS (m / z) was 639.83.

[0037] Synthesis Example 12: Synthesis of Compound 122 Under nitrogen protection, intermediate 1-5 (13.19 g, 40 mmol), N-(4-(fluoranthracene-3-yl)phenyl)-[1,1'-biphenyl]-4-amine (18.00 g, 40.4 mmol) (CAS: 2768080-78-8), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 18.47 g of compound 122, with a yield of 62.5%.

[0038] The measured value of the product by MALDI-TOF-MS (m / z) was 738.39.

[0039] Synthesis Example 13: Synthesis of Compound 145 Under nitrogen protection, intermediate 1-1 (10.19 g, 40 mmol), bis[4-(dibenzofuran-2-yl)phenyl]amine (20.26 g, 40.4 mmol) (CAS: 1228468-74-3), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 17.10 g of compound 145, with a yield of 59.4%.

[0040] The measured value of the product by MALDI-TOF-MS (m / z) was 719.50.

[0041] Synthesis Example 14: Synthesis of Compound 158 Under nitrogen protection, intermediate 1-3 (10.83 g, 40 mmol), N-([1,1'-biphenyl]-4-yl)-9-phenyldibenzothiophene-2-amine (17.27 g, 40.4 mmol) (CAS: 2922453-80-1), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 16.07 g of compound 158, with a yield of 60.7%.

[0042] The measured value of the product by MALDI-TOF-MS (m / z) was 661.86.

[0043] Synthesis Example 15: Synthesis of Compound 160 Under nitrogen protection, intermediate 1-3 (10.83 g, 40 mmol), N-[1,1'-biphenyl-4-yl]-9,9-dimethyl-9H-fluorene-2-amine (14.60 g, 40.4 mmol) (CAS: 897671-69-1), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 15.13 g of compound 160, with a yield of 63.5%.

[0044] The measured value of the product by MALDI-TOF-MS (m / z) was 595.70.

[0045] Synthesis Example 16: Synthesis of Compound 164 Under nitrogen protection, intermediates 1-3 (10.83 g, 40 mmol), N-(4-cyclohexylphenyl)-9,9-dimethyl-9H-fluorene-2-amine (14.85 g, 40.4 mmol) (CAS: 2572528-98-2), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 15.45 g of compound 164, with a yield of 64.2%.

[0046] The measured value of the product by MALDI-TOF-MS (m / z) was 601.86.

[0047] Synthesis Example 17: Synthesis of Compound 184 Under nitrogen protection, intermediate 1-6 (13.19 g, 40 mmol), N-(4-(naphthyl-1-yl)phenyl)-9-phenyl-9H-carbazole-2-amine (18.61 g, 40.4 mmol) (CAS: 1427316-59-3), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 18.94 g of compound 184, with a yield of 62.8%.

[0048] The measured value of the product by MALDI-TOF-MS (m / z) was 753.79.

[0049] Synthesis Example 18: Synthesis of Compound 188 Under nitrogen protection, intermediate 1-5 (13.19 g, 40 mmol), N-phenyl-4-(triphenylsilyl)aniline (17.28 g, 40.4 mmol) (CAS: 860465-20-9), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 17.13 g of compound 188, with a yield of 59.4%.

[0050] The measured value of the product by MALDI-TOF-MS (m / z) was 720.25.

[0051] Synthesis Example 19: Synthesis of Compound 197 Under nitrogen protection, intermediate 2-1 (10.56 g, 40 mmol), N-(4-bromophenyl)-N,N-bis(1,1'-biphenyl-4-yl)amine (19.25 g, 40.4 mmol) (CAS: 499128-71-1), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 16.53 g of compound 197, with a yield of 67.1%.

[0052] The measured value of the product by MALDI-TOF-MS (m / z) was 615.53.

[0053] The fluorescence spectrum of compound 197 was measured at room temperature in a solution with toluene as the solvent using a fluorescence spectrophotometer, with a peak fluorescence value at 475 nm. The UV spectrum of compound 197 was measured at room temperature in a solution with toluene as the solvent using a UV-Vis spectrophotometer, with a peak UV absorption value at 427 nm.

[0054] Synthesis Example 20: Synthesis of Compound 200 Under nitrogen protection, intermediate 2-1 (10.56 g, 40 mmol), N,N-bis(4-cyclohexanephenyl)-4-iodoaniline (21.63 g, 40.4 mmol) (CAS: 1287245-59-3), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 16.25 g of compound 200, with a yield of 64.7%.

[0055] The measured value of the product by MALDI-TOF-MS (m / z) was 627.93.

[0056] Synthesis Example 21: Synthesis of Compound 213 Under nitrogen protection, intermediate 2-3 (11.20 g, 40 mmol), N-([1,1'-biphenyl]-2-yl)-N-(4-bromophenyl)dibenzofuran-3-amine (CAS: 2877008-20-1) (19.61 g, 40.4 mmol), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 16.82 g of compound 213, with a yield of 65.1%.

[0057] The measured value of the product by MALDI-TOF-MS (m / z) was 645.88.

[0058] Synthesis Example 22: Synthesis of Compound 220 Under nitrogen protection, intermediates 1-2 (10.19 g, 40 mmol), N1,N1-bis(4-tert-butylphenyl)-N3-(dibenzofuran-4-yl)phenyl-1,3-diamine (21.76 g, 40.4 mmol) (CAS: 2706584-47-4), sodium tert-butoxide (7.69 g, 80 mmol), tris(dibenzylacetone)dipalladium (0.73 g, 0.8 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.46 g, 1.6 mmol) were added to 100 mL of toluene. The mixture was stirred and heated to 115 °C for 16 h. After cooling to room temperature, toluene and deionized water were added, and the mixture was stirred and separated. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Ethanol was added and heated to dissolve the filtrate. After cooling to room temperature, crystals were precipitated, filtered, and dried to obtain 17.14 g of compound 220, with a yield of 56.6%.

[0059] The measured value of the product by MALDI-TOF-MS (m / z) was 756.65.

[0060] Synthesis Example 23: Synthesis of Compound 224 Under nitrogen protection, intermediate 2-1 (10.56 g, 40 mmol), 4-(benzoxazol-2-yl)-N-(4-benzoxazol-2-yl)phenyl)-N-(4-bromophenyl)aniline (CAS: 2968456-34-8) (22.56 g, 40.4 mmol), potassium carbonate (11.06 g, 80 mmol), and tetra(triphenylphosphine)palladium (0.46 g, 0.4 mmol) were added to 100 mL of a toluene / ethanol / water mixture with a volume ratio of 2:1:1. The mixture was heated to 85 °C and stirred for 6 h. After cooling to room temperature, deionized water was added, and the mixture was filtered. The filter cake was dissolved in N-methylpyrrolidone by heat, cooled to room temperature to crystallize, filtered, and then dissolved in toluene by heat, cooled to room temperature to crystallize, filtered, and dried to obtain 16.61 g of compound 224, with a yield of 59.5%. The measured value of the product by MALDI-TOF-MS (m / z) was 697.71.

[0061] Synthesis Example 24: Synthesis of Compound 232 Under nitrogen protection, intermediate 2-4 (11.20 g, 40 mmol), N,N-bis([1,1'-biphenyl]-4-yl)-5'-chloro-[1,1':2',1''-terphenyl]-4-amine (CAS: 2983098-35-5) (23.60 g, 40.4 mmol), potassium carbonate (11.06 g, 80 mmol), and tetra(triphenylphosphine)palladium (0.46 g, 0.4 mmol) were added to 100 mL of a toluene / ethanol / water mixture with a volume ratio of 2:1:1. The mixture was heated to 85 °C and stirred for 6 h. Then, it was cooled to room temperature, deionized water was added, and the mixture was filtered. The filter cake was dissolved in N-methylpyrrolidone by heat, cooled to room temperature to crystallize, filtered, and then dissolved in toluene by heat, cooled to room temperature to crystallize, filtered, and dried to obtain 21.0 g of compound 232, with a yield of 67.0%. The measured value of the product by MALDI-TOF-MS (m / z) was 784.07.

[0062] Synthesis Example 25: Synthesis of Compound 239 Under nitrogen protection, intermediate 2-1 (10.56 g, 40 mmol), 10-bromo-N,N-di-p-tolyl-anthracene-9-amine (CAS: 223726-59-8) (18.28 g, 40.4 mmol), potassium carbonate (11.06 g, 80 mmol), and tetrakis(triphenylphosphine)palladium (0.46 g, 0.4 mmol) were added to 100 mL of a toluene / ethanol / water mixture with a volume ratio of 2:1:1. The mixture was heated to 85 °C and stirred for 6 h. After cooling to room temperature, deionized water was added, and the mixture was filtered. The filter cake was dissolved in N-methylpyrrolidone by heat, cooled to room temperature to crystallize, filtered, and then dissolved in toluene by heat, cooled to room temperature to crystallize, filtered, and dried to obtain 15.57 g of compound 239, with a yield of 65.8%. The measured value of the product by MALDI-TOF-MS (m / z) was 591.63.

[0063] Device Examples Indium tin oxide (ITO) glass substrates were ultrasonically cleaned successively in cleaning agent and deionized water for 1 h, followed by ultrasonic cleaning with acetone and isopropanol for 15 min each, vacuum dried for 2 h (105 °C), and then subjected to UV ozone treatment for 15 min. The ITO glass substrates were then transferred to a vacuum evaporation machine. 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HAT-CN) was vacuum-deposited on the ITO glass substrate to a thickness of 10 nm to form a hole injection layer; N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) was vacuum-deposited on the hole injection layer to a thickness of 40 nm to form a hole transport layer; 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline (TAPC) was vacuum-deposited on the hole transport layer to a thickness of 10 nm. A hole transport auxiliary layer is formed with a thickness of nm; a compound represented by Formula 1 in this invention, one of comparative compound 1, and bis(1-phenyl-isoquinoline)(acetylacetone)iridium(III) (Ir(piq)2acac) are vacuum-deposited on the hole transport auxiliary layer at a weight ratio of 95:5 to a thickness of 30 nm to form a light-emitting layer; 4,6-bis(3,5-di(3-pyridinylphenyl)-2-methylpyrimidine (B3PYMPM) is vacuum-deposited on the light-emitting layer to a thickness of 10 nm to form a hole blocking layer material; 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) is vacuum-deposited on the hole blocking layer to a thickness of 30 nm to form an electron transport layer material; lithium fluoride (LiF) is vacuum-deposited on the electron transport layer to a thickness of 1 nm to form an electron injection layer; aluminum (Al) is vacuum-deposited on the electron injection layer to a thickness of 100 nm to form a cathode, thereby completing the fabrication of the device.

[0064] A current was applied to each organic light-emitting device fabricated using compounds selected from Table 1, at a current of 10 mA / cm². 2 The luminescence characteristics under current density conditions were detected, and the results are shown in Table 1 below.

[0065] Table 1 Performance Characterization of Organic Electroluminescent Devices like Figure 1 The image shows the electroluminescence spectrum of the device prepared from compound 160.

[0066] The above results demonstrate that the novel aromatic amine compound constructed using a phenanthrene five-membered heterocycle with three heteroatoms at a higher triplet energy level exhibits a significant redshift in its emission spectrum due to intramolecular charge transfer (ICT) characteristics. Compared to existing aromatic amine compounds constructed using phenanthrene five-membered heterocycles with two heteroatoms, this compound, when applied to the functional layer of a device, imparts high luminous efficiency, low driving voltage, and high color purity, representing a significant advancement over existing technologies. Furthermore, compared to the heteroatom-containing compounds described in Chinese Patent (Publication No. CN116874477A) which exhibit better absorption in the ultraviolet light band (<400nm), the absorption spectrum (>500nm) of the aromatic amine compound of this invention better matches the excitation spectrum of the guest in the visible light region, making it an excellent luminescent host material.

[0067] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An aromatic amine compound, characterized in that, The compound represented by the following chemical formula 1: ； Chemical Formula 1 In the above chemical formula 1: X is one of O, S, and N(R1); Y is N; R1 is C6~C 12 aryl; Ar1 is shown in chemical formula 2: ； Chemical formula 2 In the above chemical formula 2: * indicates the connection point between Ar1 and L1; L1, L2, and L3 may be the same or different from each other, and each is independently a single bond or a C6~C bond. 18 The arylene group, wherein the arylene group is not substituted or is substituted by a C1-C4 alkyl group; Ar2 and Ar3 may be the same or different from each other, and are independently C6 to C6. 18 aryl, C6-C 24 Arylsilyl, C6~C 24 Aromatic amino groups or C6-C 12 heteroaryl groups; R2 and R3 may be the same or different from each other, and are independently C1-C1. 18 Alkyl or C6~C 12 aryl; m1 is 1 or 2; m2 and m3 may be the same or different from each other, and are independently 0, 1 or 2 respectively.

2. The aromatic amine compound according to claim 1, characterized in that, Each of the C6~C 12 The aryl group, the C6-C 18 The arylene group, the C6~C 18 The aryl group is a group formed by 1-3 benzene ring groups linked by single bonds, alkyl groups, fused ring groups or combinations thereof; The C6~C 24 The arylsilyl group is C6~C 12 A group formed by replacing three hydrogen atoms in a silyl group with any three groups in the aryl group; The C6~C 24 The aromatic amino group is C6~C 18 aryl, C6-C 12 A group formed by replacing two hydrogen atoms in an amino group with any two groups in a heteroaryl group; The C6~C 12 The heteroaryl group is a group formed by connecting 1-2 benzene ring groups and a five-membered heterocyclic group through a fused ring.

3. The aromatic amine compound according to claim 2, characterized in that, Each of the C6~C 12 The aryl group, the C6-C 18 The arylene group, the C6~C 18 The aryl groups may be the same or different from each other, and are each independently one of a monocyclic aromatic hydrocarbon group, a biphenyl-type polycyclic aromatic hydrocarbon group, or a fused-ring polycyclic aromatic hydrocarbon group; The C6~C 12 The heteroaryl group is a fused-ring polycyclic aromatic hydrocarbon group containing one of the heteroatoms O, N, and S.

4. The aromatic amine compound according to claim 3, characterized in that: The monocyclic aromatic group is phenyl; The biphenyl-type polycyclic aromatic hydrocarbon group is selected from biphenyl and terphenyl; The fused-ring polycyclic aromatic hydrocarbon group is selected from naphthyl, anthraceneyl, phenanthryl, fluoranyl, and fluorenyl. The fused-ring polycyclic aromatic hydrocarbon group is selected from indolyl, benzofuranyl, benzothiophenyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, carbazoleyl, dibenzofuranyl, and dibenzothiaphenyl.

5. The aromatic amine compound according to claim 4, characterized in that: R1 is selected from phenyl, biphenyl, and naphthyl; The L1, L2, and L3 may be the same as or different from each other, and are independently phenyl, biphenyl, terphenyl, or naphthyl, respectively, and are either unsubstituted or substituted by C1-C4 alkyl groups; The Ar2 and Ar3 may be the same as or different from each other, and are independently phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluoranyl, indolyl, benzofuranyl, benzothiophene, benzoimidazolyl, benzooxazolyl, benzothiazolyl, carbazole, dibenzofuranyl, and dibenzothiophene. R2 and R3 may be the same as or different from each other, and are independently C1-C4 alkyl groups and C6-C2 alkyl groups, respectively. 10 Cycloalkane group or C6~C 12 Aryl groups.

6. The aromatic amine compound according to claim 5, characterized in that, The C1-C4 alkyl groups are selected from one of methyl, ethyl, and tert-butyl. The C6-C 10 The cycloalkane group is selected from cyclohexyl or adamantyl; The C6~C 12 The aryl group is selected from one of phenyl, biphenyl, and naphthyl.

7. The aromatic amine compound according to claim 1, characterized in that, The aromatic amine compound is selected from compounds represented by the following chemical formulas: 。 8. An organic electroluminescent device, comprising: First electrode; A second electrode positioned relative to the first electrode; And a functional layer, wherein the functional layer is disposed between the first electrode and the second electrode; The functional layer includes the aromatic amine compound according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, characterized in that: The functional layer includes one or more of a hole transport layer, a hole transport auxiliary layer, a light-emitting layer, an electron blocking layer, and an electron transport layer, wherein at least one of the light-emitting layer, the hole transport layer, and the hole transport auxiliary layer includes an aromatic amine compound as described in any one of claims 1 to 7.

10. The organic electroluminescent device according to claim 9, characterized in that, The light-emitting layer includes a light-emitting host and a dopant, wherein the light-emitting host includes an aromatic amine compound as described in any one of claims 1 to 7.

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