A benzofuran acridine-based optoelectronic material, its preparation method and application

Abstract

The present invention relates to a benzofuran acridine-based optoelectronic material, a preparation method thereof, and an application thereof, belonging to the technical field of luminescent materials. The benzofuran acridine-based optoelectronic material is a compound with the following structure: ; Ar is selected from a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms; wherein the substituent is selected from deuterium, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a biphenyl group; the heteroatom in the heteroaryl group is selected from N, O, or S. The benzofuran acridine-based optoelectronic material is applied to the light-emitting layer of an organic electroluminescent device. The organic electroluminescent element containing the benzofuran acridine-based optoelectronic material of the present invention can be driven by a low voltage, has a higher luminous efficiency, has a longer service life, and has excellent high-temperature service life.

Description

Technical Field

[0001] The invention relates to a benzofuran acridine photoelectric material and a preparation method and application thereof, belonging to the technical field of luminescent materials. Background Art

[0002] Since 2000, OLED has been hailed as the third generation of display technology. It has received great attention from the industry due to its excellent performance that other display technologies cannot match. The rapid development of information science and technology has led to higher and higher requirements for information display devices, especially high-quality images, i.e. high resolution, high contrast, high response speed, wide viewing angle, and portability, i.e. ultra-thin, ultra-light, and low power consumption, which have become the development direction of future information display, and OLED just meets all of the above requirements.

[0003] OLED, as an electroluminescent material with a completely different luminescence mechanism, is a luminescence phenomenon produced under the action of an electric field. When OLED emits light, it is a luminescence process that directly converts electrical energy into light energy.

[0004] Compared with other display technologies, OLED has many advantages, such as a wide range of material selection, high luminous brightness and efficiency, full-color display in the blue to red spectrum, wide viewing angle, low driving voltage, relatively simple manufacturing process, low cost, and the most distinctive feature is that it can achieve flexible display. OLED can meet the requirements of higher performance and greater information capacity of display devices in today's information age, so it is imperative to develop higher performance OLED materials. Summary of the invention

[0005] The present invention aims at the deficiencies in the prior art and provides a benzofuran acridine photoelectric material and a preparation method and application thereof. The benzofuran acridine photoelectric material has excellent electroluminescent properties and can be applied to OLED to effectively prolong the service life of the device.

[0006] The technical solution of the present invention to solve the above technical problem is as follows: a benzofuran acridine photoelectric material, wherein the benzofuran acridine photoelectric material is a compound having the following structure:

[0007] ;

[0008] Ar is selected from a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms; wherein the substituent is selected from deuterium, a C1 to C4 alkyl group, a phenyl group, and a biphenyl group; and the heteroatom in the heteroaryl group is selected from N, O, and S.

[0009] Further, Ar is selected from any one of phenyl, biphenyl, naphthyl, phenanthryl, triphenylene, fluoranthene, benzanthryl, terphenyl, pyrene, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, N-phenylcarbazolyl, 9,9-diphenylfluorenyl, quinolyl, 3,5-diphenyltriazine, benzo 9,9-dimethylfluorenyl, deuterated carbazolyl, and isoquinolyl.

[0010] Further, Ar is selected from any one of the following structures:

[0011] .

[0012] Furthermore, the benzofuran acridine photoelectric material is selected from any one of the following structures:

[0013] .

[0014] The present invention also discloses a method for preparing a benzofuran acridine photoelectric material, the preparation method comprising:

[0015] ;

[0016] S1. Preparation of intermediate A:

[0017] 2-methyl-4-methoxyquinoline and triisopropyl borate are added to an organic solvent and stirred until the system is completely dissolved, the system is cooled to -5~5°C, n-butyl lithium is added dropwise to the system, and after the addition is complete, the reaction is carried out at room temperature, and the reaction is completed and post-processed to obtain intermediate A;

[0018] S2. Preparation of intermediate B:

[0019] Under the protection of inert gas, 2-bromo-5-chloro-6-fluoroiodobenzene, potassium carbonate, toluene, water, palladium acetate, and triphenylphosphine were added to the reactor, and when the temperature was raised to 60-65°C with stirring, a tetrahydrofuran solution of intermediate A was added dropwise, and the reaction was completed by heat preservation, and intermediate B was obtained after post-treatment;

[0020] S3. Preparation of intermediate C:

[0021] Under the protection of inert gas, add intermediate B and organic solvent into the reactor, then cool the system to below -80°C, add n-butyl lithium dropwise into the system, after the addition is complete, control the temperature at -85~-80°C to react for 0.5~1.5h, then heat the system to -40~-30°C, add DMF dropwise into the system, then keep the temperature for reaction again, after the reaction is complete, obtain intermediate C through post-treatment;

[0022] S4. Preparation of intermediate D:

[0023] Under the protection of inert gas, add intermediate C, potassium tert-butoxide and organic solvent into the reactor, slowly heat the system to 120-125°C, react for 5 hours, keep the temperature, and after the reaction is completed, obtain intermediate D through post-treatment;

[0024] S5. Preparation of intermediate E:

[0025] Under the protection of inert gas, add intermediate D and organic solvent into the reactor, slowly cool the system to -5~0°C, drop boron tribromide into the system, and keep the temperature below 0°C for reaction after the dropwise addition is completed. After the reaction is completed, post-treatment is performed to obtain intermediate E;

[0026] S6. Preparation of subject A or subject B:

[0027] Preparation of the main body A: Under the protection of inert gas, add the intermediate E, potassium carbonate and organic solvent into the reactor, slowly heat the system to 120-130°C for reaction, and after the reaction is completed, obtain the main body A through post-treatment;

[0028] Preparation of the main body B: under the protection of inert gas, add the main body A, biboric acid pinacol ester, potassium acetate, toluene, tetrakis(triphenylphosphine)palladium into the reactor, react at 90-100° C., and after the reaction, post-treat to obtain the main body B;

[0029] S7. Preparation of benzofuran acridine photoelectric materials:

[0030] With the main body A and arylboronic acid Ar-B(OH) 2 The benzofuran acridine photoelectric material is prepared by reacting with the main raw material; or the benzofuran acridine photoelectric material is prepared by reacting with the main raw material B and the halogenated aromatic hydrocarbon Ar-X, wherein X is selected from Cl, Br or I.

[0031] Further, in step S7, the main body A and the aromatic boronic acid Ar-B(OH) 2 When the benzofuran acridine photoelectric material is prepared by reaction as the main raw material, toluene or tetrahydrofuran is used as the solvent; potassium carbonate provides an alkaline environment; the catalyst in the reaction process is selected from a combination of palladium acetate and tri-tert-butylphosphine, a combination of tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)bispalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl; and the reaction temperature is 70-80°C.

[0032] Furthermore, in step S7, when the main body B and the halogenated aromatic hydrocarbon Ar-X are reacted as the main raw materials to prepare the benzofuran acridine photoelectric material, toluene is used as the solvent; the catalyst in the reaction process is selected from a combination of palladium acetate and tri-tert-butyl phosphine, a combination of tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)bispalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl; and the reaction temperature is 70-80°C.

[0033] The invention also discloses an application of a benzofuran acridine photoelectric material. The benzofuran acridine photoelectric material is applied to an organic electroluminescent device.

[0034] Furthermore, the organic electroluminescent device comprises at least one functional layer containing the benzofuran acridine photoelectric material.

[0035] Furthermore, the organic electroluminescent device comprises a light-emitting layer, and the light-emitting layer contains the benzofuran acridine photoelectric material.

[0036] The benzofuran acridine photoelectric material is used as a light-emitting main material or a doping material in the organic electroluminescent device.

[0037] The invention also discloses an electronic device, wherein the electronic device contains the organic electroluminescent device of the invention; the organic electroluminescent device is used for preparing lighting or display elements.

[0038] The beneficial effects of the present invention are:

[0039] The benzofuran acridine photoelectric material of the present invention has benzofuran acridine as a skeleton, connected by aromatic groups, has a deep HOMO energy level and high electron mobility, and can be used alone as a main light-emitting layer material or a light-emitting layer doping material by modification of other aromatic groups. The benzofuran acridine photoelectric material of the present invention contains a hole group structure, which can balance the electrons and holes of the material, so that the material can be used as an electron-biased material.

[0040] In addition, the benzofuran acridine photoelectric material contains a benzofuran acridine structure that destroys the molecular symmetry and avoids intermolecular aggregation. The benzofuran acridine photoelectric material group of the present invention is relatively rigid, has the characteristics of being difficult to crystallize and aggregate between molecules, and has good film-forming properties, and has a high glass transition temperature and thermal stability. Therefore, when the compound of the present invention is applied to an OLED device, the stability of the film layer after the material is formed can be maintained, thereby improving the service life of the OLED device.

[0041] After the benzofuran acridine photoelectric material of the present invention is applied to OLED devices as an organic electroluminescent functional layer material, the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the device life is significantly improved, and it has a good application effect in OLED light-emitting devices and has a good industrialization prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 A schematic diagram of the structure of an OLED device in an embodiment of the present invention;

[0043] In the figure, 1, transparent substrate layer; 2, ITO anode layer; 3, hole injection layer; 4, hole transport layer; 5, light-emitting layer; 6, electron transport layer; 7, electron injection layer; 8, cathode reflective electrode layer. DETAILED DESCRIPTION

[0044] In order to make the above-mentioned purpose, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0046] The preparation method of benzofuran acridine photoelectric material is as follows:

[0047] ;

[0048] S1. Preparation of intermediate A:

[0049] 2-Methyl-4-methoxyquinoline (CAS: 31835-53-7) is used as the starting material. The specific synthesis method is as follows: 2-methyl-4-methoxyquinoline (30 g, 173.2 mmol) and triisopropyl borate (42.3 g, 225.1 mmol) are added to 270 mL of tetrahydrofuran and stirred until the system is completely dissolved. After the dissolution is completed, the system temperature is cooled to 0°C, 83 mL of n-butyl lithium is added dropwise to the system, and after the addition is completed, the temperature is naturally raised to room temperature for reaction for 1 hour. After the reaction is completed, the reaction solution is poured into 50 mL of hydrochloric acid for hydrolysis. After the hydrolysis is completed, 250 mL of EA is added for extraction. After layering, the concentrated organic phase product is slurried with toluene to obtain 31.4 g of intermediate A (yield: 83.5%), and the purity of HPLC (intermediate A) is 99.5%.

[0050] Elemental analysis structure: molecular formula is C 11 H 12 BNO 3 ; LC-MS product molecular weight: 217.6, product theoretical molecular weight is 217.03; 1 H NMR: δ 2.59 (3H, s), 3.83 (3H, s), 6.25 (s, 2H), 7.54-7.75 (2H), 7.94 (1H, ddd), 8.27 (1H, ddd).

[0051] S2. Preparation of intermediate B:

[0052] With intermediate A and 2-bromo-5-chloro-6-fluoroiodobenzene (CAS: 1820674-47-2) as the main raw materials, 2-bromo-5-chloro-6-fluoroiodobenzene 30g (89.5mmol), potassium carbonate 24.7g (178.9mmol), toluene 300g (303.4ml), water 57.6mL, palladium acetate 0.1004g (0.4447mmol), triphenylphosphine 0.2615g (0 .8946mmol), when the temperature was raised to 60-65℃ with stirring, a tetrahydrofuran solution of intermediate A was added dropwise (19.4g (89.5mmol) intermediate A was dissolved in 60mL tetrahydrofuran), and the temperature was controlled at 60-65℃ for reaction after the addition was completed. The reaction was sampled and tracked by GC for 4h. The reaction was kept warm for 4h. The GC (2-bromo-5-chloro-6-fluoroiodobenzene) content was 1.25%, and the intermediate B content was 95.6%. After the reaction was qualified, the intermediate B was layered, washed with water, and passed through a silica gel column to obtain 26.8g of intermediate B with a GC purity of 97.6% and a yield of 78.6%.

[0053] Elemental analysis structure: molecular formula is C 17 H 12BrClFNO; GC-MS detected the product molecular weight: 381.1, the product theoretical molecular weight is 380.64; 1 H NMR: δ 2.36 (3H, s), 3.90 (3H, s), 7.27-7.62 (4H), 7.85 (1H, ddd), 7.99 (1H, ddd).

[0054] S3. Preparation of intermediate C:

[0055] Taking intermediate B and DMF as the starting main raw materials, add intermediate B 30g (78.8mmol) and tetrahydrofuran 250mL into a 500mL three-necked flask filled with nitrogen, then cool the system to below -80°C, add 90mmol of n-butyl lithium dropwise into the system, control the temperature at -85°C for 1h after the addition is complete, then naturally heat the system to -40~-30°C, add 6.9g (94.6mmol) of DMF dropwise into the system, then keep warm for 1h, hydrolyze, wash with water, remove solvent, and recrystallize from petroleum ether to obtain 22.1g of intermediate C with a GC purity of 98.9% and a yield of 85%.

[0056] Elemental analysis structure: molecular formula is C 18 H 13 ClFNO 2 ; GC-MS detected the product molecular weight: 315.2, the product theoretical molecular weight is 329.76; 1 H NMR: δ 2.46 (3H, s), 3.98 (3H, s), 7.39 (1H, ddd), 7.54-7.71(2H), 7.90-8.20 (3H), 10.08 (1H, s).

[0057] S4. Preparation of intermediate D:

[0058] Take intermediate C as raw material, add intermediate C 30g (91mmol), 15.3g (136.5mmol) potassium tert-butoxide and DMF 200mL into a 500mL three-necked flask filled with nitrogen, slowly heat the system to 120-125℃, react for 5h, follow up detection GC (intermediate C) ≤2% qualified, after the reaction is qualified, hydrolyze, alkalize, wash with water, column and recrystallize to obtain intermediate D 20.7g, with a yield of 72.9%.

[0059] Elemental analysis structure: molecular formula is C 18 H 11 ClFNO; GC-MS detected the product molecular weight: 311.5, the product theoretical molecular weight is 311.74; 1H NMR: δ 3.95 (3H, s), 7.37 (1H, ddd), 7.54-7.73 (3H), 7.92-8.32(4H).

[0060] S5. Preparation of intermediate E:

[0061] Take intermediate D as raw material, add intermediate D 30g (96.2mmol) and dichloroethane 200mL into a 500mL three-necked flask filled with nitrogen, slowly cool the system to -5°C, add boron tribromide 26.5g (105.8mmol) dropwise into the system, and after the addition is complete, react at below 0°C for 1h, and follow-up detection GC (intermediate D) ≤0.5% is qualified. After the reaction is qualified, it is hydrolyzed, alkalized, washed with water, and desolvated to obtain intermediate E 26.8g with a yield of 93.5%.

[0062] Elemental analysis structure: molecular formula is C 17 H 9 ClFNO; GC-MS detected the product molecular weight: 297.3, the product theoretical molecular weight is 297.71; 1 H NMR: δ 7.36 (1H, ddd), 6.53(1H), 7.58-7.74 (2H), 7.86-8.32 (5H).

[0063] S6. Preparation of subject A or subject B:

[0064] Preparation of subject A: Using intermediate E as raw material, add intermediate F 30g (100.8mmol), potassium carbonate 20.8g (151.2mmol), DMF 200mL into a 500mL three-necked flask filled with nitrogen, slowly heat the system to 130℃ and react for 1h, follow up detection GC (intermediate E) ≤1% qualified, after the reaction is qualified, filter, remove solvent, wash with hot water, pass column, remove solvent, recrystallize from 2 times xylene to obtain 17.8g of subject A, GC (substance A) purity is 99.5%, and the yield is 63.5%.

[0065] Elemental analysis structure: molecular formula is C 17 H 8 ClNO; GC-MS detected the product molecular weight: 277.1, the product theoretical molecular weight is 277.71; 1 H NMR: δ 7.76 (1H, dd), 7.85-8.05 (3H), 8.12 (1H, dd), 8.35 (1H, ddd), 8.55 (1H, ddd), 8.83 (1H, ddd).

[0066] Preparation of subject B: Using subject A as raw material, add subject A 30g (108mmol), bipyraclostrobin 27.4g (108mmol), potassium acetate 15.9g (162mmol), toluene 250mL, tetrakis(triphenylphosphine)palladium 1.25g (1.08mmol) into a 500mL three-necked flask filled with nitrogen, heat the system to 90-100℃ and react for 5h. After hydrolysis, washing, desolvation, and recrystallization from 2 times toluene, 32.9g of subject B is obtained. The GC (substrate B) purity is 99.7%, and the yield is 82.5%.

[0067] Elemental analysis structure: molecular formula is C 23 H 20 BNO 3 ; GC-MS detected the product molecular weight: 369.5, the product theoretical molecular weight is 369.23; 1 H NMR: δ 1.38 (12H, s), 7.83-8.12 (3H), 8.20 (1H, dd), 8.41 (1H,ddd, ), 8.58-8.78 (3H).

[0068] S7. Preparation of benzofuran acridine photoelectric materials:

[0069] With the main body A and arylboronic acid Ar-B(OH) 2 The benzofuran acridine photoelectric material is prepared by reacting with the main raw material; or the benzofuran acridine photoelectric material is prepared by reacting with the main raw material B and the halogenated aromatic hydrocarbon Ar-X, wherein X is selected from Cl, Br or I.

[0070] Specifically, in step S7, the main body A and the aromatic boronic acid Ar-B(OH) 2 When the benzofuran acridine photoelectric material is prepared by reaction as the main raw material, toluene or tetrahydrofuran is used as a solvent; potassium carbonate provides an alkaline environment; the catalyst in the reaction process is selected from a combination of palladium acetate and tri-tert-butylphosphine, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)bispalladium (hereinafter referred to as Pd 2 (dba) 3 The reaction mixture is prepared by combining 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (hereinafter referred to as X-PHOS); the reaction temperature is 70-80°C.

[0071] Specifically, in step S7, when the main body B and the halogenated aromatic hydrocarbon Ar-X are reacted as the main raw materials to prepare the benzofuran acridine photoelectric material, toluene is used as the solvent; the catalyst in the reaction process is selected from a combination of palladium acetate and tri-tert-butyl phosphine, a combination of tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)bispalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl; the reaction temperature is 70-80°C.

[0072] Example 1: Preparation of Compound 1

[0073] ;

[0074] Synthesis of compound 1: 27.8 g of main body A, 12.1 g of phenylboric acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene, and 0.578 g of tetrakis(triphenylphosphine)palladium were added to a 500 mL three-necked flask, and the temperature was raised to 70°C under stirring under a nitrogen atmosphere for reaction. The reaction was completed in 3 hours. After the reaction was completed, the system was separated into layers. The organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 23.3 g of compound 1 as a white solid, HPLC: 99.96%, yield 73%.

[0075] Elemental analysis structure: molecular formula is C 23 H 13 NO; LC-MS detected the product molecular weight: 319.2, the product theoretical molecular weight is 319.36; 1 H NMR: δ 7.64-7.78 (3H), 7.97-8.11 (3H), 8.23 ​​(1H,ddd), 8.47 (1H,dd), 8.62 (1H, ddd), 8.69-8.82 (2H), 9.05 (1H, ddd), 9.17 (1H, dd).

[0076] Example 2: Preparation of Compound 11

[0077] ;

[0078] Synthesis of compound 11: 27.8 g of main body A, 22.2 g of 9-phenanthreneboric acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene, and 0.578 g of tetrakis(triphenylphosphine)palladium were added to a 500 mL three-necked flask, and the mixture was stirred and heated to 70°C under a nitrogen atmosphere for reaction. The reaction was completed in 3 hours. After the reaction was completed, the system was separated into layers. The organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 23.2 g of compound 11 as a white solid, HPLC: 99.97%, yield 55.4%.

[0079] Elemental analysis structure: molecular formula is C 31 H 17 NO; LC-MS detected the product molecular weight: 419.3, the theoretical molecular weight of the product is 419.48; 1 H NMR: δ 7.85-8.20 (4H), 8.34-8.55 (2H), 8.57-8.73(4H), 8.76-9.10(4H), 9.11-9.31 (3H).

[0080] Example 3: Preparation of Compound 16

[0081] ;

[0082] Synthesis of compound 16: 27.8 g of main body A, 27.4 g of 1,1':4',1" terphenyl-2-boric acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene and 0.578 g of tetrakis(triphenylphosphine)palladium were added to a 500 mL three-necked flask, and the mixture was stirred and heated to 70°C under a nitrogen atmosphere for reaction. The reaction was completed in 3 h. After the reaction was completed, the system was separated and the organic phase was washed with water, desolvated, recrystallized from toluene and dried to obtain 32.5 g of compound 16 as a white solid, HPLC: 99.991%, yield 69%.

[0083] Elemental analysis structure: molecular formula is C 35 H 21 NO; LC-MS detected the product molecular weight: 471.41, the product theoretical molecular weight is 471.56; 1 H NMR: δ 7.53-7.82 (4H), 7.83-8.14 (6H), 8.33-8.58(5H), 8.75-9.08(4H), 9.15-9.30 (2H).

[0084] Example 4: Preparation of Compound 18

[0085] ;

[0086] Synthesis of compound 18: 27.8 g of main body A, 24.6 g of 2-fluoranthene boronic acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene and 0.578 g of tetrakis(triphenylphosphine)palladium were added to a 500 mL three-necked flask, and the mixture was stirred and heated to 70°C under a nitrogen atmosphere. The reaction was completed in 3 hours. After the reaction was completed, the system was separated and the organic phase was washed with water, desolvated, recrystallized from toluene and dried to obtain 34.6 g of compound 18 as a white solid, HPLC: 99.95%, yield 78%.

[0087] Elemental analysis structure: molecular formula is C 33 H 17 NO; LC-MS detected the product molecular weight: 471.41, the theoretical molecular weight of the product is 443.5; 1 H NMR: δ 7.73 (1H, ddd), 7.80-7.95 (2H), 8.28 (1H, d), 8.34-8.53(4H), 8.56-8.73 (2H), 8.77-9.08 (5H), 9.16-9.30 (2H).

[0088] Example 5: Preparation of Compound 33

[0089] ;

[0090] Synthesis of compound 33: 27.8 g of main body A, 21.2 g of 2-dibenzofuranboronic acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene, 0.225 g of palladium acetate and 0.953 g of X-PHOS were added to a 500 mL three-necked flask, and the mixture was stirred and heated to 65 °C under a nitrogen atmosphere. The reaction was completed in 2 h. After the reaction was completed, the system was separated and the organic phase was washed with water, desolvated, recrystallized from toluene and dried to obtain 26.1 g of compound 33 as a white solid, HPLC: 99.989%, yield 63.8%.

[0091] Elemental analysis structure: molecular formula is C 29 H 15 NO 2 ; LC-MS detected the product molecular weight: 409.21, the theoretical molecular weight of the product is 409.44; 1 H NMR: δ 7.79-8.17 (5H), 8.20-8.34 (2H), 8.41-8.89(6H), 9.10-9.26(2H).

[0092] Example 6: Preparation of Compound 37

[0093] ;

[0094] Synthesis of compound 37: 27.8 g of main body A, 24.6 g of 1-pyreneboric acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene, and Pd 2 (dba) 3 0.458 g of 2-nitropropene and 0.953 g of X-PHOS were added into a 500 mL three-necked flask, and the mixture was stirred and heated to 75 °C under a nitrogen atmosphere. The reaction was completed after 8 h. After the reaction was completed, the system was separated into layers. The organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 33.9 g of compound 37 as a white solid. HPLC: 99.93%, yield 76.4%.

[0095] Elemental analysis structure: molecular formula is C 33 H 17 NO; LC-MS detected the product molecular weight: 443.8, the product theoretical molecular weight is 443.51; 1 H NMR: δ 8.32 (1H, tt), 8.47 (1H, dd), 8.67 (2H, td), 8.78-9.30 (13H).

[0096] Example 7: Preparation of Compound 41

[0097] ;

[0098] Synthesis of compound 41: 27.8 g of main body A, 23.8 g of 9,9-dimethylfluorene-2-boric acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene and 0.578 g of tetrakis(triphenylphosphine)palladium were added to a 500 mL three-necked flask, stirred and heated to 70°C under a nitrogen atmosphere for reaction. The reaction was completed in 4 hours. After the reaction was completed, the system was separated and the organic phase was washed with water, desolvated, recrystallized from toluene and dried to obtain 30.5 g of compound 41 as a white solid, HPLC: 99.99%, yield 70%.

[0099] Elemental analysis structure: molecular formula is C 32 H 21 NO; LC-MS detected the product molecular weight: 435.4, the product theoretical molecular weight is 435.53; 1 H NMR: δ 2.07 (6H, s), 7.47-7.68 (4H), 8.06-8.39 (3H), 8.42-8.55(2H), 8.55-8.86 (3H), 8.87-9.20 (3H).

[0100] Example 8: Preparation of Compound 48

[0101] ;

[0102] Synthesis of compound 48: 27.8 g of main body A, 22.8 g of 3-dibenzothiopheneboric acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene, and 0.578 g of tetrakis(triphenylphosphine)palladium were added to a 500 mL three-necked flask, and the mixture was stirred and heated to 70°C under a nitrogen atmosphere. The reaction was completed after 10 hours. After the reaction was completed, the system was separated and the organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 28.3 g of compound 48 as a white solid, HPLC: 99.98%, yield 66.5%.

[0103] Elemental analysis structure: molecular formula is C 32 H 15 NOS; LC-MS detected the product molecular weight: 425.0, the product theoretical molecular weight is 425.51; 1 H NMR: δ 7.79-8.15 (3H), 8.21-8.34 (2H), 8.36-8.88(7H), 8.95 (1H,ddd), 9.06-9.26 (2H).

[0104] Example 9: Preparation of Compound 50

[0105] ;

[0106] Synthesis of compound 50: 27.8 g of main body A, 28.7 g of N-phenylcarbazole-3-boric acid, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene, and 0.578 g of tetrakis(triphenylphosphine)palladium were added to a 500 mL three-necked flask, and the mixture was stirred and heated to 70°C under a nitrogen atmosphere for reaction. The reaction was completed in 3 hours. After the reaction was completed, the system was separated into layers. The organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 35.6 g of compound 50 as a white solid, HPLC: 99.94%, yield 73.6%.

[0107] Elemental analysis structure: molecular formula is C 35 H 20 N 2 O; LC-MS detected the product molecular weight: 424.20, the theoretical molecular weight of the product is 484.56; 1 H NMR: δ 7.54 (1H, tdd), 7.65-8.05 (7H), 8.21-8.37(3H), 8.37-8.60(2H), 8.70-9.01 (5H), 9.07-9.23 (2H).

[0108] Example 10: Preparation of Compound 71

[0109] ;

[0110] Synthesis of compound 71: 28.7 g of main body B, 26.8 g of 3,5-diphenyl-1-chlorotriazine, 13.2 g of potassium carbonate, 30.8 g of water, 240 g of toluene, and Pd 2 (dba) 3 0.458 g of 2-nitropropene and 0.953 g of X-PHOS were added into a 500 mL three-necked flask, and the mixture was heated to 70 °C under stirring under a nitrogen atmosphere. The reaction was completed after 3 h. After the reaction was completed, the system was separated into layers. The organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 35.8 g of compound 71 as a white solid. HPLC: 99.97%, yield 75.4%.

[0111] Elemental analysis structure: molecular formula is C 32 H 18 N 4 O; LC-MS detected the product molecular weight: 474.3, the theoretical molecular weight of the product is 474.52; 1 H NMR: δ 7.90-8.10 (6H), 8.31-8.48 (5H), 8.71-8.98(4H), 9.09 (1H,ddd), 9.31-9.52 (2H).

[0112] Example 11: Preparation of Compound 72

[0113] ;

[0114] Synthesis of compound 72: 27.8 g of main body A, 17.5 g of d8-carbazole, 13.2 g of potassium carbonate, 240 g of DMF, 2 g of cuprous iodide and 1.8 g of N,N-dimethylethylenediamine were added to a 500 mL three-necked flask, heated to 130°C with stirring under a nitrogen atmosphere, and the reaction was completed after 15 hours. After the reaction, the system was filtered, and the organic phase was extracted, washed with water, desolventized, recrystallized from toluene, and dried to obtain 27.7 g of compound 72 as a white solid, HPLC: 99.98%, yield 66.5%.

[0115] Elemental analysis structure: molecular formula is C 29 H 8 D 8 N 2 O; LC-MS detected the product molecular weight: 416.1, the theoretical molecular weight of the product is 416.51; 1 H NMR: δ 7.63-7.53 (3H), 8.00-7.92 (3H), 8.08-8.01(1H), 8.22-8.15(1H).

[0116] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device embodiments 1 to 11 and device comparative example 1. The device manufacturing process of device embodiments 2 to 11 and device comparative example 1 is exactly the same as that of device embodiment 1, and the same substrate material and electrode material are used. The film thickness of the electrode material is also the same. The difference is that the light-emitting layer material in the device is changed in device embodiments 2 to 11.

[0117] Device Example 1:

[0118] like Figure 1 As shown, an organic electroluminescent device, the preparation steps of which include:

[0119] a) cleaning the ITO anode layer 2 on the transparent substrate layer 1 by ultrasonic cleaning with deionized water, acetone, and ethanol for 15 minutes each, and then treating it in a plasma cleaner for 2 minutes;

[0120] b) On the ITO anode layer 2, a hole injection layer 3 material HAT-CN is deposited by vacuum evaporation with a thickness of 10 nm, and this layer serves as the hole injection layer 3;

[0121] c) On the hole injection layer 3, a hole transport material NPB is deposited by vacuum evaporation with a thickness of 80 nm, and this layer is the hole transport layer 4;

[0122] d) Evaporating the light-emitting layer 5 on the hole transport layer 4, wherein the main materials are the compound 1 of the present invention and the compound GH, and the doping material is Ir(ppy) 3 , compound 1, GH and Ir(ppy) 3 The mass ratio of the three is 50:50:10, and the thickness is 30nm;

[0123] e) On the light-emitting layer 5, an electron transport material TPBI is deposited by vacuum evaporation with a thickness of 40 nm. This layer of organic material is used as the electron transport layer 6;

[0124] f) On the electron transport layer 6, the electron injection layer 7 material LiF is vacuum evaporated to a thickness of 1 nm, and this layer is the electron injection layer 7;

[0125] g) On the electron injection layer 7 , cathode Al (100 nm) is vacuum-deposited. This layer serves as the cathode reflective electrode layer 8 .

[0126] After the electroluminescent device is fabricated according to the above steps, the driving voltage, current efficiency, device life, and device life at 85°C are measured. The results are shown in Table 1. The molecular structure formula of the relevant material is shown below:

[0127] .

[0128] Device Example 2:

[0129] ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HATCN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 11, GH and Ir(ppy) 3 The composition is composed of a mixed structure in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).

[0130] Device Example 3:

[0131] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HAT-CN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound 16, GH and Ir(ppy) 3 The composition is composed of a mixed structure in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).

[0132] Device Example 4:

[0133] ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HATCN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 18, GH and Ir(ppy) 3 The composition is composed of a mixed structure in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).

[0134] Device Example 5:

[0135] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound 33, GH and Ir(ppy)3 mixed in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0136] Device Example 6:

[0137] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound 37, GH and Ir(ppy)3 mixed in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0138] Device Example 7:

[0139] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound 41, GH and Ir(ppy)3 mixed in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0140] Device Example 8:

[0141] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound 48, GH and Ir(ppy)3 mixed in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0142] Device Example 9:

[0143] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound 50, GH and Ir(ppy)3 mixed in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0144] Device Example 10:

[0145] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound 71) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0146] Device Example 11:

[0147] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound 72) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0148] Device Comparison Example 1:

[0149] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compound HB, GH and Ir(ppy)3 mixed in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0150] Device Comparison Example 2:

[0151] ITO anode layer 2 (thickness: 150nm) / hole injection layer 3 (thickness: 10nm, material: HATCN) / hole transport layer 4 (thickness: 80nm, material: NPB) / light-emitting layer 5 (thickness: 40nm, material: compounds HC, GH and Ir(ppy)3 mixed in a weight ratio of 50:50:10) / electron transport layer 6 (thickness: 35nm, material: TPBI) / electron injection layer 7 (thickness: 1nm, material: LiF) / Al (thickness: 100nm).

[0152] The organic electroluminescent devices prepared in the above device embodiments and device comparative examples were subjected to performance testing, and the specific data are shown in Table 1.

[0153] Table 1 Performance test data of organic electroluminescent devices

[0154]

[0155] From the results in Table 1, it can be seen that the benzofuran acridine photoelectric material of the present invention can be used to make OLED light-emitting devices, and compared with the device comparison example, the device driving voltage using the benzofuran acridine photoelectric material of the present invention is much lower than the device comparison example. In addition, both the efficiency and lifespan are greatly improved compared with the known device comparison example OLED materials, especially the service life of the device is greatly improved. Further, its service life is tested at high temperature. It can be seen from Table 1 that device embodiments 1 to 9 are device structures in which the benzofuran acridine photoelectric material of the present invention is matched with known materials, and device embodiments 10 to 11 are device structures in which the benzofuran acridine photoelectric material of the present invention is used as the main light-emitting material. Compared with the device comparison example, the OLED device provided by the present invention has a good service life at high temperature.

[0156] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0157] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A benzofuran acridine photoelectric material, characterized in that: The benzofuran acridine photoelectric material is a compound having the following structure: ； The Ar is selected from any one of phenyl, biphenyl, naphthyl, phenanthryl, triphenylene, fluoranthene, benzanthryl, terphenyl, pyrene, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, N-phenylcarbazolyl, 9,9-diphenylfluorenyl, 3,5-diphenyltriazine, benzo-9,9-dimethylfluorenyl and deuterated carbazolyl.

2. The benzofuran acridine photoelectric material according to claim 1, characterized in that: The Ar is selected from any one of the following structures: 。 3. A benzofuran acridine photoelectric material, characterized in that: The benzofuran acridine photoelectric material is selected from any one of the following structures: 。 4. A method for preparing a benzofuran acridine photoelectric material according to claim 1, characterized in that: The preparation method is: ； S1. Preparation of intermediate A: 2-methyl-4-methoxyquinoline and triisopropyl borate are added to an organic solvent and stirred until the system is completely dissolved, the system is cooled to -5~5°C, n-butyl lithium is added dropwise to the system, and after the addition is complete, the reaction is carried out at room temperature, and the reaction is completed and post-processed to obtain intermediate A; S2. Preparation of intermediate B: Under the protection of inert gas, 2-bromo-5-chloro-6-fluoroiodobenzene, potassium carbonate, toluene, water, palladium acetate, and triphenylphosphine were added to the reactor, and when the temperature was raised to 60-65°C with stirring, a tetrahydrofuran solution of intermediate A was added dropwise, and the reaction was completed by heat preservation, and intermediate B was obtained after post-treatment; S3. Preparation of intermediate C: Under the protection of inert gas, add intermediate B and organic solvent into the reactor, then cool the system to below -80°C, add n-butyl lithium dropwise into the system, after the addition is complete, control the temperature at -85~-80°C to react for 0.5~1.5h, then heat the system to -40~-30°C, add DMF dropwise into the system, then keep the temperature for reaction again, after the reaction is complete, obtain intermediate C through post-treatment; S4. Preparation of intermediate D: Under the protection of inert gas, add intermediate C, potassium tert-butoxide and organic solvent into the reactor, slowly heat the system to 120-125°C, react for 5 hours, keep the temperature, and after the reaction is completed, obtain intermediate D through post-treatment; S5. Preparation of intermediate E: Under the protection of inert gas, add intermediate D and organic solvent into the reactor, slowly cool the system to -5~0°C, drop boron tribromide into the system, and keep the temperature below 0°C for reaction after the dropwise addition is completed. After the reaction is completed, post-treatment is performed to obtain intermediate E; S6. Preparation of subject A or subject B: Preparation of the main body A: Under the protection of inert gas, add the intermediate E, potassium carbonate and organic solvent into the reactor, slowly heat the system to 120-130°C for reaction, and after the reaction is completed, obtain the main body A through post-treatment; Preparation of the main body B: under the protection of inert gas, add the main body A, biboric acid pinacol ester, potassium acetate, toluene, tetrakis(triphenylphosphine)palladium into the reactor, react at 90-100° C., and after the reaction, post-treat to obtain the main body B; S7. Preparation of benzofuran acridine photoelectric materials: A benzofuran acridine photoelectric material is prepared by reacting a main body A and an aromatic boronic acid Ar-B(OH)2 as main raw materials; or a benzofuran acridine photoelectric material is prepared by reacting a main body B and a halogenated aromatic hydrocarbon Ar-X as main raw materials, wherein X is selected from Cl, Br or I, and Ar is as defined in claim 1.

5. The method for preparing a benzofuran acridine photoelectric material according to claim 4, characterized in that: In step S7, when the main raw materials A and arylboronic acid Ar-B(OH)2 are reacted to prepare benzofuran acridine photoelectric materials, toluene or tetrahydrofuran is used as solvent; potassium carbonate provides an alkaline environment; the reaction temperature is 70-80°C; In step S7, when the main raw materials B and halogenated aromatic hydrocarbon Ar-X are reacted to prepare benzofuran acridine photoelectric materials, toluene is used as solvent; and the reaction temperature is 70-80°C.

6. An application of a benzofuran acridine photoelectric material according to any one of claims 1 to 3, characterized in that: The benzofuran acridine photoelectric material is applied to organic electroluminescent devices.

7. The use of a benzofuran acridine photoelectric material according to claim 6, characterized in that: The organic electroluminescent device comprises at least one functional layer containing the benzofuran acridine photoelectric material.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a light-emitting layer, and the light-emitting layer contains the benzofuranacridine photoelectric material according to any one of claims 1 to 3.

9. An electronic device, characterized in that: The electronic device comprises the organic electroluminescent device according to claim 8.

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