A material with benzopyridine-acridine structure and its application

Abstract

The present invention relates to a material of a benzopyridine acridine structure and its application, belonging to the technical field of OLED materials. The material of the benzopyridine acridine structure is as follows: Ar is any one of a C6-C36 aryl group, a heterocyclic aryl group, a deuterated substituted aryl group or a deuterated substituted heterocyclic aryl group, and the heteroatom in the heterocyclic aryl group is selected from N, S, and O. The material of the benzopyridine acridine structure is used in an OLED device as a main material of a light-emitting layer. The material containing the benzopyridine acridine structure has a special structure, better energy level and stacking structure of the compound, better thermal stability and higher electron mobility, and exhibits excellent performance in OLED devices, including extending the working life, improving luminous efficiency and reducing driving pressure.

Description

Technical Field

[0001] The invention relates to a material with a benzopyridine-acridine structure and application thereof, belonging to the technical field of OLED materials. Background Art

[0002] Organic light emitting diodes (OLED) have the advantages of self-luminescence, wide viewing angle, short response time, high luminous efficiency, thin panel, low energy consumption, and wide operating temperature range. Currently, OLED displays are gradually replacing LCD displays and becoming the mainstream display. The core material layers in OLED devices are the light-emitting layer, electron transport layer, and hole transport layer. Among them, the most core part is the light-emitting layer. The organic electroluminescent material used in it determines the luminous efficiency, film forming properties, and carrier transport properties of OLED devices.

[0003] The light-emitting layer of an OLED device is excited by the recombination of injected carriers, and then emits light with high efficiency. Therefore, the light-emitting layer must use compounds with very strong fluorescence or phosphorescence. Although other layers can use inorganic substances, the light-emitting layer must be organic.

[0004] With the rapid development of OLED devices, people have higher and higher demands on the luminous performance of display devices. Therefore, it is of great value to develop organic electroluminescent materials with better performance. Summary of the invention

[0005] The present invention aims at the deficiencies in the prior art and provides a material with a benzopyridine-acridine structure and an application thereof. The material with a benzopyridine-acridine structure has good thermal stability and high electron affinity, and has excellent performance in optoelectronic devices.

[0006] The technical solution of the present invention to solve the above technical problem is as follows: a material with a benzopyridine-acridine structure, wherein the material with a benzopyridine-acridine structure is shown in general formula I:

[0007] Formula I;

[0008] Ar is any one of a C6-C36 aryl group, a heterocyclic aryl group, a deuterated aryl group or a deuterated substituted heterocyclic aryl group, and the heteroatom in the heterocyclic aryl group is selected from N, S and O.

[0009] Further, Ar is selected from any one of the following groups:

[0010] ;

[0011] .

[0012] Furthermore, the material of the benzopyridine-acridine structure is selected from any one of the following structural formulas:

[0013] ;

[0014] ;

[0015] .

[0016] An application of a material with a benzopyridine-acridine structure, wherein the material with a benzopyridine-acridine structure is applied to an OLED device.

[0017] Furthermore, the material with the benzopyridine-acridine structure is applied to the light-emitting layer in an OLED device.

[0018] Furthermore, the material with the benzopyridine-acridine structure is used as a main material of the light-emitting layer in an OLED device.

[0019] The beneficial effects of the present invention are:

[0020] The benzopyridine-acridine structured material has a special structure, better compound energy levels and stacking structures, better thermal stability and higher electron mobility, and exhibits excellent performance in OLED devices, including extending the working life, improving luminous efficiency and reducing driving pressure.

[0021] The acridine structure in the benzopyridine acridine structure material has unique electrical properties, electrochemical properties, and photophysical properties. Acridine, as a nitrogen-containing heteroaromatic ring, has the following characteristics: it is easy to form stable positive ions; it has a large conjugated system and strong intramolecular electron transfer in the molecule; it has high thermal stability and photochemical stability. The pyridine structure is a highly fluorescent compound with a high electron affinity, which is conducive to the injection of electrons and has a strong blue fluorescence. After it is connected with the acridine structure, the electron affinity of the molecule is significantly increased, causing the photoelectric properties of the entire molecule to change. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a schematic structural diagram of the OLED device of the present invention;

[0023] In the figure, 1, TFT substrate; 2, anode layer; 3, hole injection layer; 4, hole transport layer; 5, light emitting layer; 6, electron transport layer; 7, electron injection layer; 8, cathode. DETAILED DESCRIPTION

[0024] 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.

[0025] 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.

[0026] Synthesis method of universal intermediates of parent structure:

[0027] ;

[0028] (1) Synthesis of intermediate 1: 50 mmol of sodium m-nitrobenzenesulfonate (CAS: 127-68-4), 100 mmol of ferrous sulfate heptahydrate, and 200 mmol of methanesulfonic acid were added to the reaction flask; 100 mmol of m-bromoaniline (CAS: 591-19-5) was added dropwise under nitrogen, the temperature was raised to 110.0-120.0°C, 110 mmol of glycerol was added dropwise, and the temperature was kept for 5 h after the addition. After the reaction was completed, the reaction system was hydrolyzed and the solvent was removed to obtain the product with a yield of 95%. Mass spectrum: m / z = 207.00; hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d )δ 8.87 (dd, J = 7.5, 1.6 Hz, 1H), 8.30 (dt, J = 7.3, 1.5 Hz, 1H), 8.20 (d, J = 1.7Hz, 1H), 7.84 (dd, J = 7.5, 1.5 Hz, 1H), 7.62 (dd, J = 7.6, 1.6 Hz, 1H), 7.35 (t, J = 7.5 Hz, 1H).

[0029] (2) Synthesis of intermediate 2: 40 mmol of intermediate 1, 100 g of dichloroethane (as solvent), and 160 mmol of sulfuric acid were added to the reaction flask, and then nitrogen was passed through. 42 mmol of nitric acid was added dropwise at a temperature of 10-15°C. After the addition, the temperature was kept for 2 hours. After the reaction was completed, the reaction solution was added to ice water for hydrolysis, washed with water, and recrystallized from ethyl acetate to obtain the product with a yield of 73%. Mass spectrum: m / z=251.70; Hydrogen spectrum: 1 HNMR (500 MHz, Chloroform- d ) δ 8.95 (dd, J = 7.6, 1.4 Hz, 1H), 8.20 (dt, J = 7.5,1.6 Hz, 1H), 8.11 (dd, J = 7.4, 1.5 Hz, 1H), 7.77 (d, J = 7.5 Hz, 1H), 7.52 (t, J =7.4 Hz, 1H).

[0030] (3) Synthesis of intermediate 3: 49.5 mmol of intermediate 2, 74.3 mmol of potassium carbonate, 20 g of water and 100 g of tetrahydrofuran were added to the reaction flask, 0.5 mmol of palladium acetate and 1.0 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthene were added under nitrogen, and then the temperature was raised to 55-60°C and the solution (50 mmol of 2-fluoro-3-chlorophenylboronic acid (CAS: 352535-82-1) dissolved in 50 g of tetrahydrofuran) was added dropwise. After the addition was completed, the temperature was kept for 8 hours, and after hydrolysis, toluene was added for extraction, washed with water, passed through a silica gel column, desolventized, and recrystallized from toluene to obtain intermediate 3 with a yield of 69%. Mass spectrum: m / z = 302.10; hydrogen spectrum: 1 H NMR (500MHz, Chloroform- d ) δ 9.02 (dd, J = 7.5, 1.6 Hz, 1H), 8.37 (dt, J = 7.4, 1.4 Hz,1H), 8.04 (dd, J = 7.5, 1.6 Hz, 1H), 7.76 (dd, J = 7.5, 2.1 Hz, 1H), 7.58 (t, J =7.5 Hz, 1H), 7.49 (ddd, J = 7.0, 5.0, 1.7 Hz, 1H), 7.45 – 7.34 (m, 2H).

[0031] (4) Synthesis of intermediate 4: 102 mmol of iron powder, 20 g of water and 100 g of tetrahydrofuran were added to the reaction flask, nitrogen was introduced, 2 g of hydrochloric acid (30% concentration) was added dropwise at a temperature of 50-55°C, and then the solution (51 mmol of intermediate 3 dissolved in 20 g of tetrahydrofuran) was added dropwise. After the addition was completed, the mixture was kept warm for 2 h, sodium hydroxide was added to adjust the pH to 7, and intermediate 4 was obtained after filtration, toluene extraction, water washing and solvent removal, with a yield of 95%. Mass spectrum: m / z = 272.09; hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.71 (dd, J =7.5, 1.2 Hz, 1H), 8.27 (dt, J = 7.6, 1.6 Hz, 1H), 7.65 (dd, J = 7.5, 1.6 Hz, 1H),7.59 – 7.46 (m, 3H), 7.44 – 7.34 (m, 2H), 6.20 (d, J = 9.6 Hz, 1H), 6.14 (d, J =9.9 Hz, 1H).

[0032] (5) Synthesis of intermediate 5: 48 mmol of intermediate 4, 144 mmol of cesium carbonate and 30 g of N,N-dimethylformamide were added to the reaction flask, and then the temperature was raised to 150-155°C and kept for 15 hours. Then, it was hydrolyzed, and then toluene was added for extraction, washed with water, passed through a silica gel column, desolventized, and recrystallized from ethyl acetate to obtain intermediate 4 with a yield of 78%. Mass spectrum: m / z=252.10; hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 10.46 (s, 1H), 8.81 (dd, J = 7.6, 1.5 Hz,1H), 8.34 (dq, J = 7.3, 1.1 Hz, 1H), 7.88 (dd, J = 7.4, 1.6 Hz, 1H), 7.83 (d, J =1.1 Hz, 2H), 7.54 – 7.44 (m, 1H), 7.39 (t, J = 7.4 Hz, 1H), 7.32 (dd, J = 7.2,1.5 Hz, 1H).

[0033] (6) Synthesis of intermediate 6: 44 mmol of intermediate 5, 66 mmol of biboronic acid pinacol ester, 52.8 mmol of potassium acetate, and 100 g of xylene were added to the reaction flask, and then nitrogen was passed through. 0.5 mmol of tris(dibenzylideneacetone)dipalladium and 1.0 mmol of tricyclohexylphosphine were added, and the temperature was raised to 130-135°C for reaction. The temperature was kept for 12 hours, and then hydrolyzed, washed with water, passed through a silica gel column, desolventized, and recrystallized from xylene to obtain intermediate 6 with a yield of 76%. Mass spectrum: m / z=344.25; hydrogen spectrum: 1 H NMR (500MHz, Chloroform- d ) δ 10.60 (s, 1H), 8.80 (dd, J = 7.4, 1.3 Hz, 1H), 8.40 – 8.34(m, 1H), 7.94 – 7.87 (m, 2H), 7.78 (dd, J = 7.6, 1.6 Hz, 1H), 7.49 (t, J = 7.4Hz, 1H), 7.43 (dd, J = 7.3, 1.5 Hz, 1H), 7.29 (t, J = 7.5 Hz, 1H), 1.24 (s, 12H).

[0034] (7) Synthesis of intermediate 7: 80.0 mmol of 8-bromonaphthalene-1-amine (CAS: 62456-34-2) and 100 g of dichloroethane were added to the reaction flask, and 80.0 mmol of N-chlorosuccinimide was added to the reaction system at a temperature of 0-10 °C, and then kept warm for 5 h. After hydrolysis, washing, passing through a silica gel column, removing the solvent, and recrystallization using dichloroethane, intermediate 7 was obtained. The yield was 79%. Mass spectrum: m / z = 257.0; hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.06 (dd, J = 7.4, 1.3 Hz, 1H),7.49 – 7.40 (m, 2H), 7.32 (t, J = 7.4 Hz, 1H), 7.00 (d, J = 7.6 Hz, 1H), 5.32 (s, 2H).

[0035] (8) Synthesis of intermediate 8: 70.0 mmol of intermediate 7 and 100 g of glacial acetic acid were added to the reaction flask, the temperature was raised to 70-75°C, 50 g of sulfuric acid aqueous solution (30% concentration) was added, the temperature was kept for 1 h, then the temperature was lowered to 0-10°C, 73.5 mmol of sodium nitrite aqueous solution (30% concentration) was added dropwise at a controlled temperature, the temperature was kept for 1 h after the addition, and then the reaction solution was added dropwise to the prepared 84 mmol of potassium iodide aqueous solution (30% concentration) at a controlled temperature of 40-50°C, the temperature was kept for 2 h, and then toluene was added for extraction after hydrolysis, washed with water, passed through a silica gel column, desolventized, and recrystallized from toluene to obtain intermediate 8. Yield: 75%. Mass spectrum: m / z = 367.8; hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.07 (dd, J = 7.6, 1.6 Hz, 1H), 7.82 (d, J = 7.6 Hz,1H), 7.68 (dd, J = 7.2, 1.5 Hz, 1H), 7.45 – 7.37 (m, 2H).

[0036] (9) Synthesis of intermediate 9: 77.5 mmol of potassium carbonate, 25 g of water and 200 g of dioxane were added to the reaction flask, 0.5 mmol of palladium acetate and 1.0 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthene were added under nitrogen, and then the temperature was raised to 90-95°C, and the mixed solution (48.0 mmol of intermediate 6 and 45.7 mmol of intermediate 8 dissolved in 500 g of dioxane) was added dropwise. After the addition was completed, the mixture was kept warm for 8 h, hydrolyzed, and then cooled to 20-25°C for filtration. The obtained solid was then washed with water for 3-5 times, and then dissolved in toluene and passed through a silica gel column. After desolvation and recrystallization, intermediate 9 was obtained. Yield: 74%. Mass spectrum: m / z=457.77; Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 11.19 (s, 1H), 8.79 (dd, J = 7.2,1.5 Hz, 1H), 8.33 (dt, J = 7.7, 1.6 Hz, 1H), 8.25 (dd, J = 7.2, 1.5 Hz, 1H), 7.98(dd, J = 7.4, 1.4 Hz, 1H), 7.89 (d, J = 7.3 Hz, 1H), 7.85 (dd, J= 7.4, 1.3 Hz,1H), 7.72 (dd, J = 7.6, 1.5 Hz, 1H), 7.60 – 7.50 (m, 4H), 7.45 (dt, J = 20.2, 7.4 Hz, 2H);

[0037] (10) Synthesis of intermediate 10: 38.6 mmol of intermediate 9, 96.5 mmol of cesium carbonate and 100 g of N-methylpyrrolidone were added to the reaction flask, then nitrogen was passed through, 0.4 mmol of palladium acetate and 0.8 mmol of tri-tert-butylphosphine tetrafluoroborate were added, the temperature was raised to 155-160°C for reaction, and the temperature was kept for 12 h. Then, after hydrolysis, filtration, dissolution with toluene, silica gel column, solvent removal, and recrystallization with o-dichlorobenzene, the fine intermediate 10 was obtained, with a final yield of 73%. Mass spectrum: m / z=376.09; hydrogen spectrum: 1 HNMR (500 MHz, Chloroform- d ) δ 8.79 (dd, J = 7.6, 1.5 Hz, 1H), 8.61 (dd, J = 7.6,1.5 Hz, 1H), 8.49 (dd, J = 7.3, 1.3 Hz, 1H), 8.36 (dt, J = 7.5, 1.5 Hz, 1H), 8.23(dd, J = 7.2, 1.5 Hz, 1H), 7.98 (dd, J = 7.5, 1.5 Hz, 1H), 7.83 (dd, J = 7.6, 1.6Hz, 1H), 7.82 – 7.76 (m, 2H), 7.73 (t, J = 7.4 Hz, 1H), 7.59 (t, J = 7.4 Hz, 1H),7.56 – 7.48 (m, 2H);

[0038] (11) Synthesis of intermediate 11: 43.8 mmol of intermediate 10, 65.7 mmol of biboric acid pinacol ester, 52.6 mmol of potassium acetate and 100 g of xylene were added to the reaction flask, and then nitrogen was passed through. 0.5 mmol of tris(dibenzylideneacetone)dipalladium and 1.0 mmol of tricyclohexylphosphine were added, and the temperature was raised to 130-135°C for reaction. The temperature was kept for 12 hours, and then hydrolyzed, washed with water, passed through a silica gel column, desolventized, and recrystallized using xylene to obtain the fine intermediate 11 with a final yield of 85%. Mass spectrum: m / z = 468.10; hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.76 (dd, J = 7.2, 1.5 Hz, 1H), 8.62 (dd, J =7.2, 1.5 Hz, 1H), 8.45 – 8.39 (m, 1H), 8.35 (dd, J = 7.4, 1.6 Hz, 1H), 8.29(dd, J = 7.6, 1.5 Hz, 1H), 8.08 (d, J = 7.6 Hz, 1H), 7.88 (dd, J = 7.6, 1.6 Hz,1H), 7.83 – 7.75 (m, 2H), 7.63 (d, J = 7.5 Hz, 1H), 7.62 – 7.57 (m, 2H), 7.53(t, J = 7.6 Hz, 1H), 1.24 (s, 12H).

[0039] The benzopyridine acridine structure material is synthesized by coupling intermediate 10 with Ar-Y (Y is a structural group such as a boronic acid group, a boronic ester group, an imine structural group, etc. that can react with a halogen group) or by coupling intermediate 11 with Ar-X (X is a common halogen group and other structural groups that can react with a boronic ester). The following are synthesis examples of several compounds:

[0040] Example 1: A structural formula of compound 1 used in OLED devices:

[0041] ;

[0042] The specific synthetic route of compound 1 is:

[0043] ;

[0044] Preparation of compound 1: 43 mmol of intermediate 10, 107.5 mmol of potassium carbonate, 35 g of water and 150 g of toluene were added to the reaction flask, then nitrogen was passed through, 0.4 mmol of tetrakistriphenylphosphine palladium was added, and then the temperature was raised to 60-65°C, and phenylboric acid solution (a solution prepared by 45.2 mmol of phenylboric acid (CAS: 98-80-6) and 20 g of tetrahydrofuran) was added dropwise, and the temperature was kept for 5 hours after the addition, and then the aqueous phase was separated by standing, and the organic phase was washed with water until it was approximately neutral, and then passed through a silica gel column, the solvent was removed, and ethyl acetate was used for recrystallization to obtain the product with a yield of 77%. Mass spectrum: m / z=418.20. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.79(dd, J = 7.4, 1.3 Hz, 1H), 8.62 (dd, J = 7.2, 1.5 Hz, 1H), 8.49 (dd, J = 7.4, 1.4Hz, 1H), 8.43 – 8.37 (m, 1H), 8.19 (dd, J = 7.6, 1.5 Hz, 2H), 8.03 (d, J = 7.6Hz, 1H), 7.85 (dd, J = 7.4, 1.5 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.69 – 7.50 (m, 6H), 7.49 – 7.42 (m, 2H), 7.42 – 7.35 (m, 1H).

[0045] Example 2: A structural formula of compound 2 used in OLED devices:

[0046] ;

[0047] The specific synthetic route of compound 2 is:

[0048] ;

[0049] Preparation of compound 2: 43 mmol of intermediate 10, 107.5 mmol of potassium carbonate, 35 g of water and 150 g of toluene were added to the reaction flask, then nitrogen was passed through, 0.4 mmol of palladium acetate and 0.8 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene were added, and then the temperature was raised to 70-75°C, and 2-biphenylboronic acid solution (a solution prepared by 45.2 mmol of 2-biphenylboronic acid (CAS: 4688-76-0) and 20 g of ethanol) was added dropwise, and the temperature was kept for 5 hours after the addition, and then the aqueous phase was separated by standing, and the organic phase was washed with water until it was approximately neutral, and then passed through a silica gel column, the solvent was removed, and toluene was used for recrystallization to obtain the product with a yield of 73%. Mass spectrum: m / z=494.48. Hydrogen spectrum: 1 HNMR (500 MHz, Chloroform- d ) δ 8.75 (dd, J = 7.3, 1.5 Hz, 1H), 8.63 (dd, J = 7.6,1.5 Hz, 1H), 8.46 – 8.40 (m, 1H), 8.37 (dd, J = 7.4, 1.4 Hz, 1H), 8.26 (dd, J =7.6, 1.5 Hz, 1H), 8.22 – 8.17 (m, 1H), 7.93 (d, J = 7.6 Hz, 1H), 7.86 (dd, J =7.5, 1.4 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.73 – 7.65 (m, 2H), 7.65 – 7.57(m, 3H), 7.57 – 7.42 (m, 7H), 7.40 – 7.32 (m, 1H).

[0050] Example 3: A structural formula of compound 5 used in OLED devices:

[0051] ;

[0052] The specific synthetic route of compound 5 is:

[0053] ;

[0054] Preparation of compound 5: Add 38.1mmol of intermediate 11, 41.9mmol of 3,5-diphenylchlorobenzene (CAS: 126866-34-0), 95.3mmol of potassium carbonate, 25g of water and 150g of toluene to the reaction flask, then pass nitrogen, add 0.4mmol of palladium acetate and 0.8mmol of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene. Keep the reaction at 75-80℃ for 15h, then separate the aqueous phase, wash the organic phase with water until it is approximately neutral, then pass through a silica gel column, remove the solvent, and use toluene for recrystallization to obtain the product with a yield of 82%. Mass spectrum: m / z=570.21. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.75 (dd, J = 7.6,1.5 Hz, 1H), 8.62 (dd, J = 7.3, 1.5 Hz, 1H), 8.46 – 8.40 (m, 1H), 8.39 – 8.32(m, 2H), 8.25 (dd, J = 7.6, 1.4 Hz, 1H), 8.20 (dd, J = 7.2, 1.5 Hz, 1H), 7.90(dd, J = 7.2, 1.3 Hz, 1H), 7.83 – 7.75 (m, 4H), 7.69 (t, J = 7.4 Hz, 1H), 7.65 –7.56 (m, 6H), 7.53 (t, J = 7.4 Hz, 1H), 7.45 – 7.33 (m, 6H).

[0055] Example 4: A structural formula of compound 6 used in OLED devices:

[0056] ;

[0057] The specific synthetic route of compound 6 is:

[0058] ;

[0059] Preparation of compound 6: 43 mmol of intermediate 10, 107.5 mmol of potassium carbonate, 35 g of water and 100 g of tetrahydrofuran were added to the reaction flask, then nitrogen was passed through, 0.4 mmol of tetrakistriphenylphosphine palladium was added, and then the temperature was raised to 60-65°C, and 1-naphthaleneboric acid solution (a solution prepared by 45.2 mmol of 1-naphthaleneboric acid (CAS: 13922-41-3) and 20 g of tetrahydrofuran) was added dropwise, and the temperature was kept for 5 hours after the addition, and then toluene was added for extraction, and the organic phase was washed with water to about neutrality, passed through a silica gel column, and the solvent was removed. The product was recrystallized using dichloroethane, and the yield was 77%. Mass spectrum: m / z=468.17. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ8.76 (dd, J = 7.2, 1.5 Hz, 1H), 8.63 (dd, J = 7.6, 1.5 Hz, 1H), 8.42 (dt, J = 7.7,1.7 Hz, 1H), 8.35 (dd, J = 7.3, 1.5 Hz, 1H), 8.23 ​​– 8.16 (m, 2H), 8.13 (d, J =7.2 Hz, 1H), 8.00 – 7.94 (m, 1H), 7.92 (dt, J = 7.6, 1.7 Hz, 1H), 7.86 (dt, J =7.4, 1.7 Hz, 2H), 7.80 (d, J = 7.6 Hz, 1H), 7.74 – 7.67 (m, 2H), 7.63 – 7.43 (m, 6H).

[0060] Example 5: A structural formula of compound 8 used in OLED devices:

[0061] ;

[0062] The specific synthetic route of compound 8 is:

[0063] ;

[0064] Preparation of compound 8: 38.1mmol of intermediate 11, 40mmol of 9-bromoanthracene (CAS: 1564-64-3), 95.3mmol of potassium carbonate, 20g of water and 200g of toluene were added to the reaction flask, then nitrogen was passed through, 0.4mmol of tetrakistriphenylphosphine palladium was added, and the reaction was kept at 80-85℃ for 12h, and then the aqueous phase was separated, and the organic phase was washed with water to about neutrality, and then passed through a silica gel column, the solvent was removed, and DMF was used for recrystallization to obtain the product with a yield of 69%. Mass spectrum: m / z=518.21. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.75 (dd, J = 7.3, 1.5 Hz, 1H), 8.63 (dd, J = 7.6, 1.5 Hz, 1H),8.43 (dt, J = 7.3, 1.6 Hz, 1H), 8.39 – 8.34 (m, 2H), 8.24 (ddd, J = 14.3, 7.4,1.6 Hz, 2H), 8.12 – 8.05 (m, 2H), 8.05 – 8.00 (m, 2H), 7.96 (d, J = 7.3 Hz,1H), 7.88 (dd, J = 7.7, 1.6 Hz, 1H), 7.80 (d, J = 7.2 Hz, 1H), 7.73 – 7.66 (m,2H), 7.61 (t, J = 7.4 Hz, 1H), 7.57 – 7.48 (m, 1H), 7.48 – 7.42 (m, 4H).

[0065] Example 6: A structural formula of compound 10 used in OLED devices:

[0066] ;

[0067] The specific synthetic route of compound 10 is:

[0068] ;

[0069] Preparation of compound 10: 43 mmol of intermediate 10, 107.5 mmol of sodium carbonate, 35 g of water and 100 g of dioxane were added to the reaction flask, then nitrogen was passed through, 0.4 mmol of tetrakistriphenylphosphine palladium was added, and then the temperature was raised to 80-85°C, and 2-benzofuran boronic acid solution (a solution made of 45.2 mmol of 2-benzofuran boronic acid (CAS: 98437-24-2) and 20 g of dioxane) was added dropwise, and the temperature was kept for 5 hours after the addition, and then toluene was added for extraction, and the organic phase was washed with water to about neutrality, passed through a silica gel column, and the solvent was removed. Toluene was used for recrystallization to obtain the product with a yield of 71%. Mass spectrum: m / z=458.21. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.76 (dd, J = 7.6, 1.5 Hz, 1H), 8.61 (dd, J = 7.4, 1.3 Hz, 1H), 8.45 – 8.40(m, 1H), 8.35 (dd, J = 7.4, 1.6 Hz, 1H), 8.25 (dd, J = 7.2, 1.5 Hz, 1H), 8.16(dd, J = 7.6, 1.6 Hz, 1H), 8.10 (d, J = 7.2 Hz, 1H), 7.94 – 7.85 (m, 2H), 7.81(dd, J = 12.0, 7.4 Hz, 2H), 7.63 – 7.50 (m, 3H), 7.43 (dd, J = 6.7, 2.4 Hz, 1H),7.34 – 7.24 (m, 2H), 7.19 (d, J = 1.5 Hz, 1H).

[0070] Example 7: A structural formula of compound 19 used in OLED devices:

[0071] ;

[0072] The specific synthetic route of compound 19 is:

[0073] ;

[0074] Preparation of compound 19: 38.1mmol of intermediate 11, 40mmol of 3-chloro-9-phenyl-9H-carbazole (CAS: 193686-61-2), 95.3mmol of potassium carbonate, 20g of water and 200g of toluene were added to the reaction flask, and then nitrogen was passed through, 0.4mmol of palladium acetate and 0.8mmol of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene were added, and the reaction was kept at 80-85℃ for 20h, and then the aqueous phase was separated, and the organic phase was washed with water until it was approximately neutral, and then passed through a silica gel column, the solvent was removed, and xylene was used for recrystallization to obtain the product with a yield of 78%. Mass spectrum: m / z=583.20. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.75 (dd, J =7.6, 1.5 Hz, 1H), 8.62 (dd, J = 7.2, 1.5 Hz, 1H), 8.46 – 8.40 (m, 1H), 8.39 –8.31 (m, 2H), 8.21 (ddd, J = 8.8, 7.4, 1.5 Hz, 2H), 8.09 (dd, J = 5.3, 3.4 Hz,1H), 7.94 – 7.87 (m, 2H), 7.80 (d, J = 7.3 Hz, 1H), 7.72 (d, J = 1.5 Hz, 1H),7.66 – 7.43 (m, 10H), 7.37 – 7.30 (m, 1H), 7.29 (dd, J = 5.7, 3.4 Hz, 2H).

[0075] Example 8: A structural formula of compound 26 used in OLED devices:

[0076] ;

[0077] The specific synthetic route of compound 26 is:

[0078] ;

[0079] Preparation of compound 26: Add 38.1mmol of intermediate 11, 40mmol of 4-bromo-9,9'-spirobi[fluorene] (CAS: 1161009-88-6), 87.8mmol of potassium carbonate, 16g of water and 150g of tetrahydrofuran to the reaction flask, then pass nitrogen, and add 0.4mmol of tetrakistriphenylphosphine palladium. Keep the reaction at 65-70℃ for 10h, add toluene to extract and then separate the aqueous phase, wash the organic phase with water until it is approximately neutral, then pass through a silica gel column, remove the solvent, and use toluene for recrystallization to obtain the product with a yield of 79%. Mass spectrum: m / z=656.33. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.75 (dd, J = 7.6, 1.5 Hz, 1H),8.63 (dd, J = 7.6, 1.5 Hz, 1H), 8.43 (dt, J = 7.6, 1.7 Hz, 1H), 8.40 – 8.34 (m,2H), 8.20 (dd, J = 7.3, 1.5 Hz, 1H), 7.90 (dd, J = 7.6, 1.4 Hz, 1H), 7.87 – 7.73(m, 5H), 7.67 – 7.57 (m, 4H), 7.52 (qd, J = 7.5, 2.2 Hz, 3H), 7.35 (td, J = 7.6,1.7 Hz, 2H), 7.29 (tdd, J = 7.3, 3.4, 1.5 Hz, 3H), 6.91 (dd, J = 7.5, 1.6 Hz,1H), 6.86 (dd, J = 7.4, 1.7 Hz, 1H), 6.80 (dd, J = 7.5, 1.7 Hz, 2H).

[0080] Example 9: A structural formula of compound 32 used in OLED devices:

[0081] ;

[0082] The specific synthetic route of compound 32 is:

[0083] ;

[0084] Preparation of compound 32: 38.1mmol of intermediate 11, 41.9mmol of 2-biphenyl-4-chloro-6-phenyl-1,3,5-triazine (CAS: 1472062-94-4), 114.3mmol of potassium carbonate, 25g of water and 200g of toluene were added to the reaction flask, and then nitrogen was passed through, and 0.4mmol of tetrakistriphenylphosphine palladium was added. The reaction was kept at 80-85℃ for 18h, and then the aqueous phase was separated, and the organic phase was washed with water until it was approximately neutral, and then passed through a silica gel column, the solvent was removed, and the product was recrystallized using xylene and ethyl acetate, and the yield was 81%. Mass spectrum: m / z=649.22. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.75 (dd, J = 7.6, 1.5 Hz,1H), 8.65 (dd, J = 7.3, 1.5 Hz, 1H), 8.59 – 8.52 (m, 2H), 8.43 (dt, J = 7.7, 1.7Hz, 1H), 8.36 (dd, J = 7.6, 1.6 Hz, 1H), 8.26 (dd, J = 7.2, 1.5 Hz, 1H), 8.03(dd, J = 8.3, 7.4 Hz, 2H), 7.90 (dd, J = 7.3, 1.5 Hz, 1H), 7.85 (d, J = 7.6 Hz,1H), 7.83 – 7.77 (m, 2H), 7.77 – 7.71 (m, 2H), 7.66 (t, J = 7.4 Hz, 1H), 7.63 –7.56 (m, 4H), 7.53 (t, J = 7.4 Hz, 1H), 7.50 – 7.39 (m, 5H), 7.39 – 7.31 (m, 1H).

[0085] Example 10: A structural formula of compound 39 used in OLED devices:

[0086] ;

[0087] The specific synthetic route of compound 39 is:

[0088] ;

[0089] Preparation of compound 39: Add 38.1mmol of intermediate 11, 38.1mmol of 9-chloro-2-phenyl-phenanthro[3,4-d]oxazole (CAS: 2085325-16-0), 95.3mmol of potassium carbonate, 25g of water and 200g of toluene to the reaction flask, then pass nitrogen, and add 0.4mmol of tetrakistriphenylphosphine palladium. Keep the reaction at 80-85℃ for 15h, then separate the aqueous phase, wash the organic phase with water until it is approximately neutral, then pass through a silica gel column, remove the solvent, and use xylene for recrystallization to obtain the product with a yield of 86%. Mass spectrum: m / z=635.22. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 9.56 (d, J = 1.4 Hz, 1H), 8.82 (s, 1H), 8.75 (dd, J = 7.6, 1.5 Hz, 1H), 8.62 (dd, J = 7.2, 1.5 Hz, 1H), 8.43 (dt, J = 7.7,1.7 Hz, 1H), 8.36 (dd, J = 7.6, 1.6 Hz, 1H), 8.35 – 8.29 (m, 2H), 8.21 (ddd, J =8.8, 7.6, 1.5 Hz, 2H), 8.13 – 8.05 (m, 3H), 7.90 (dd, J = 7.2, 1.6 Hz, 1H),7.88 – 7.83 (m, 1H), 7.80 (d, J = 7.3 Hz, 1H), 7.78 – 7.71 (m, 2H), 7.69 – 7.60(m, 3H), 7.53 (t, J = 7.6 Hz, 1H), 7.42 (qd, J = 4.5, 1.9 Hz, 3H).

[0090] Example 11: A structural formula of compound 43 used in OLED devices:

[0091] ;

[0092] The specific synthetic route of compound 43 is:

[0093] ;

[0094] Preparation of compound 43: Add 43mmol of intermediate 10, 43mmol of diphenylamine (CAS: 37055-51-9), 64.5mmol of sodium tert-butoxide and 200g of toluene to the reaction flask, then pass nitrogen, add 0.4mmol of tris(dibenzylideneacetone)dipalladium and 0.8mmol of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene. Keep the reaction at 100-105℃ for 15h, cool to below 80℃, then hydrolyze, separate the aqueous phase, wash the organic phase with water until it is approximately neutral, then pass through a silica gel column, remove the solvent, and use xylene for recrystallization to obtain the product with a yield of 81%. Mass spectrum: m / z=519.33. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.75 (dd, J = 7.6, 1.5 Hz, 1H), 8.60 (dd, J = 7.2, 1.5 Hz, 1H),8.46 – 8.40 (m, 1H), 8.36 (dd, J = 7.4, 1.3 Hz, 1H), 8.22 (dd, J = 7.6, 1.5 Hz,1H), 7.90 (dd, J = 7.1, 1.6 Hz, 1H), 7.84 – 7.78 (m, 2H), 7.73 (t, J = 7.4 Hz,1H), 7.64 (t, J = 7.6 Hz, 1H), 7.53 (t, J = 7.6 Hz, 1H), 7.43 (d, J = 7.7 Hz, 1H),7.38 (d, J = 7.6 Hz, 1H).

[0095] Example 12: A structural formula of compound 49 used in OLED devices:

[0096] ;

[0097] The specific synthetic route of compound 49 is:

[0098] ;

[0099] Preparation of compound 49: Add 43mmol of intermediate 10, 43mmol of deuterated carbazole (CAS: 38537-24-5), 64.5mmol of sodium tert-butoxide, 200g of toluene to the reaction flask, then pass nitrogen, add 0.4mmol of tris(dibenzylideneacetone)dipalladium, 0.8mmol of 2-dicyclohexylphosphine-2',6'-dimethoxy-biphenyl. Keep the reaction at 100-105℃ for 12h, cool to below 80℃, then hydrolyze, separate the aqueous phase, wash the organic phase with water until it is approximately neutral, then pass through a silica gel column, remove the solvent, and use dichloroethane for recrystallization to obtain the product with a yield of 86%. Mass spectrum: m / z=515.63. Hydrogen spectrum: 1 H NMR (500 MHz, Chloroform- d ) δ 8.75 (dd, J = 7.6, 1.5 Hz, 1H), 8.60 (dd, J = 7.2, 1.5 Hz, 1H), 8.46 – 8.40(m, 1H), 8.36 (dd, J = 7.5, 1.3 Hz, 1H), 8.22 (dd, J = 7.6, 1.5 Hz, 1H), 8.09(dd, J = 7.6, 1.6 Hz, 1H), 7.90 (dd, J = 7.3, 1.5 Hz, 1H), 7.83 – 7.76 (m, 2H), 7.69 (t, J = 7.4 Hz, 1H), 7.66 – 7.57 (m, 2H), 7.53 (t, J = 7.7 Hz, 1H).

[0100] The material based on the benzopyridine acridine structure can have a structural formula of any one of 1 to 50:

[0101] ;

[0102] ;

[0103] .

[0104] The synthesis methods of compounds 1 to 50 can refer to the above examples. For the same reaction type, the reaction conditions can be repeated. The reaction substances, generated substances and yields of each example are summarized in Table 1.

[0105] Table 1 Reaction substances, product substances and yields of synthesized compounds 1 to 50

[0106]

[0107] Device Example:

[0108] Typical structure of OLED device is as follows: Figure 1 . Usually, an anode layer 2 (ITO glass) is first arranged on a TFT substrate 1, and then a hole injection layer 3 (HIT) is plated on the anode layer 2 in sequence, followed by a hole transport layer 4 (HTL), a light emitting layer 5 (EML), an electron transport layer 6 (ETL) and an electron injection layer 7 (EIL), and finally a metal layer (Al) is added as a conductive cathode 8 and a sealing ring. The following present invention uses a material with a benzopyridine acridine structure as an example of a light emitting layer 5 to study the performance of an applied device.

[0109] Device Comparison Example 1:

[0110] Preparation of OLED material devices: (1) ITO substrate anode layer 2: The ITO anode layer 2 on the transparent TFT substrate 1 was first cleaned with distilled water for 15 minutes, then ultrasonically cleaned with isopropyl alcohol and acetone for 15 minutes, and finally treated with a plasma cleaner for 5 minutes. Then, the hole injection layer 3 material 2-TNATA was evaporated by vacuum evaporation with a thickness of 300Å. Then, the hole transport layer 4 was made of a-NPD with a thickness of 200Å. Then, the light-emitting layer 5 uses AND (9,10-bis(2-naphthyl)anthracene) or any one of the materials of the benzopyridine acridine structure described in the present invention as the main material and is mixed with 5% of the doping material TPPDA (N1, N1, N6, N6-tetraphenylpyrene-1, 6-diamine) to a thickness of 200Å and then evaporated, followed by the electron transport layer 6 and the electron injection layer 7TPBi300Å, and the cathode 8 LiF2000Å; the organic matter evaporation rate in the above process is maintained at 1Å / sec, LiF is 0.2Å / sec, and Al is 3-7Å / sec, and then the OLED light-emitting device is manufactured.

[0111] Device Example 1:

[0112] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 1 of synthesis example 1 of the present invention.

[0113] Device Example 2:

[0114] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 2 of synthesis example 2 of the present invention.

[0115] Device Example 3:

[0116] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 5 of synthesis example 3 of the present invention.

[0117] Device Example 4:

[0118] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 6 of synthesis example 4 of the present invention.

[0119] Device Example 5:

[0120] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 8 of synthesis example 5 of the present invention.

[0121] Device Example 6:

[0122] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 10 of synthesis example 6 of the present invention.

[0123] Device Example 7:

[0124] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 19 of synthesis example 7 of the present invention.

[0125] Device Example 8:

[0126] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 26 of synthesis example 8 of the present invention.

[0127] Device Example 9:

[0128] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 32 of synthesis example 9 of the present invention.

[0129] Device Example 10:

[0130] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 39 of synthesis example 10 of the present invention.

[0131] Device Example 11:

[0132] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 43 of synthesis example 11 of the present invention.

[0133] Device Example 12:

[0134] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 49 of synthesis example 12 of the present invention.

[0135] Device Example 13:

[0136] The difference between this embodiment and device comparison example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 15 synthesized by the present invention.

[0137] Device Example 14:

[0138] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 31 synthesized in the present invention.

[0139] Device Example 15:

[0140] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 36 synthesized by the present invention.

[0141] Device Example 16:

[0142] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 41 synthesized by the present invention.

[0143] Device Example 17:

[0144] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 45 synthesized by the present invention.

[0145] Device Example 18:

[0146] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 46 synthesized by the present invention.

[0147] Device Example 19:

[0148] The difference between this embodiment and device comparison example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 47 synthesized by the present invention.

[0149] Device Example 20:

[0150] The difference between this embodiment and device comparative example 1 is that the main material of the light-emitting layer of the electroluminescent device is compound 50 synthesized by the present invention.

[0151] The device performance of device examples 1-20 was tested, and the specific test results are shown in the following Table 2.

[0152] Table 2 OLED device performance test data

[0153]

[0154] Note: The test was performed using a Keithley 2400 source measurement unit and a CS-2000 spectroradiometer.

[0155] The device performance test results are referenced to Comparative Example 1, and the performance indicators of Comparative Example 1 are set to 1.0. It can be seen from the test results in the above table that the device to which the novel material of the present invention is applied has a longer life and improved luminous efficiency. The OLED device prepared by the novel material of benzopyridine acridine structure of the present invention has excellent performance in all aspects and great potential in application.

[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 material having a benzopyridine-acridine structure, characterized in that: The material of the benzopyridine acridine structure is shown in the general formula I: Formula I; The Ar is selected from any one of the following groups: 。 2. A material having a benzopyridine-acridine structure, characterized in that: The material of the benzopyridine acridine structure is selected from any one of the following structural formulas: 。 3. An application of a material having a benzopyridine-acridine structure according to any one of claims 1 to 2, characterized in that: The material of the benzopyridine-acridine structure is applied to the light-emitting layer in an OLED device.

4. The use of a material having a benzopyridine-acridine structure according to claim 3, characterized in that: The material with the benzopyridine-acridine structure is used as the main material of the light-emitting layer in an OLED device.

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