Luminescent compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic photoelectric materials, and discloses an organic light-emitting compound and application thereof in an electroluminescent device. The chemical structure of the organic light-emitting compound meets the following general formula. According to the light-emitting compound provided by the invention, 2-position or 3-position methyl of anthracene can improve the solubility of a material, reduce the synthesis and purification cost of the material, reduce aggregation among molecules, avoid fluorescence quenching caused by molecular accumulation and realize high exciton utilization rate; the connection site of anthracene and the # imgabs0 # unit is relatively twisted, so that the steric hindrance of molecular space is increased, molecular aggregation can be inhibited, and the constructed compound is beneficial to preparation of a blue organic light-emitting diode with high efficiency and long service life. # imgabs1 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic photoelectric materials, and in particular relates to a class of organic luminescent compounds and their application in electroluminescent devices. Background Art

[0002] Organic light-emitting diodes (OLEDs) have the advantages of flexibility, active luminescence, high efficiency, low voltage drive, and easy preparation of large-area devices, and have attracted widespread attention. OLED-related research can be traced back to the 1960s. In 1963, Professor Pope of New York University and others first discovered the electroluminescence phenomenon of organic molecule single crystal anthracene. Subsequently, some studies on the electroluminescence properties of single crystal structure materials appeared one after another. However, due to the high device driving voltage at that time, it did not attract widespread attention. It was not until 1987 that Deng Qingyun and others from Kodak Company in the United States developed an OLED device using a sandwich device structure, with a brightness of 1000cd m2 driven by a 10V DC voltage. -2 , which has brought about a revolutionary development in OLED research.

[0003] Organic light-emitting diodes have two main application prospects: one is in new display, and the other is in solid-state lighting. The luminescent material is the core part of OLED, which determines the color of the device and, to a large extent, the efficiency and life of the device. To achieve a full-color display panel with a high color rendering index, organic luminescent materials that emit red, green and blue are required. Compared with green and red light materials, high-efficiency blue fluorescent materials are still relatively scarce. Therefore, the development of new high-performance blue light materials is a research focus of OLED research. Summary of the invention

[0004] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a class of luminescent compounds. This class of organic luminescent compounds includes methyl-substituted anthracene units, naphthalene, anthracene, etc., which are units with wide band gap, high stability, high fluorescence quantum yield, and high carrier mobility, and conjugated units. Further improve the molecular charge transport performance. The methyl group of the anthracene unit and the anthracene The unit connection sites lead to increased molecular steric hindrance, which can inhibit molecular aggregation. The constructed compounds are conducive to the preparation of high-efficiency and long-life blue light-emitting organic diodes.

[0005] Another object of the present invention is to provide a method for preparing the light-emitting polymer.

[0006] Another object of the present invention is to provide application of the above-mentioned luminescent compound in electroluminescent devices, especially in blue light emitting diodes.

[0007] The purpose of the present invention is achieved by at least one of the following technical solutions.

[0008] A type of luminescent compound, characterized in that its chemical structure satisfies the following general formula:

[0009]

[0010] Preferably, the chemical structure of the luminescent compound satisfies one of the following general formulas:

[0011]

[0012] Wherein, X is O, S, NR, C-(R)2, wherein R is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms;

[0013] Ar is a H atom or an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms;

[0014] The unit is an aromatic hydrocarbon group having 12 to 60 carbon atoms or an aromatic heterocyclic group having 12 to 60 carbon atoms.

[0015] Furthermore, Ar, in addition to being a H atom, is preferably the following structure:

[0016]

[0017]

[0018] Furthermore, the above-mentioned luminescent compound is characterized in that The unit is preferably of the following structure:

[0019]

[0020]

[0021] Preferably, the luminescent compound is at least one of the following structures:

[0022]

[0023]

[0024] The above-mentioned luminescent compound is a blue light compound.

[0025] A method for preparing the above-mentioned luminescent compound comprises the following steps:

[0026]

[0027] (1) 4-(2-naphthyl)phenylboronic acid and 9,10-dibromo-2-methylanthracene undergo a one-sided Suzuki coupling reaction to obtain compound 1;

[0028] (2) Compound 1 and a boronic acid or boronic acid ester functional group The unit was subjected to a second Suzuki coupling to obtain the target compound.

[0029] Furthermore, the preparation method of the above-mentioned luminescent compound is characterized by:

[0030] In step (1), the reaction molar ratio of 4-(2-naphthyl)phenylboronic acid to 9,10-dibromo-2-methylanthracene is 0.2:1 to 2:1, preferably 0.5:1 to 1:1, the reaction temperature is preferably 60 to 120° C., and the reaction time is preferably 2 to 24 hours.

[0031] In step (2), compound 1 and a boronic acid or boronic acid ester functional group are reacted The reaction molar ratio of the units is preferably 1:1 to 1:2, the reaction temperature is preferably 60 to 120° C., and the reaction time is preferably 2 to 24 hours.

[0032] The above-mentioned light-emitting compounds are used in organic electroluminescent devices, especially in blue light-emitting diodes.

[0033] Furthermore, the use of the above-mentioned type of luminescent compound in an organic electroluminescent device is characterized in that the organic electroluminescent device comprises a substrate, an anode layer, an organic layer and a cathode layer;

[0034] The organic layer includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer;

[0035] The organic light-emitting layer is at least one of the light-emitting compounds mentioned above.

[0036] Furthermore, the application of the above-mentioned luminescent compounds in organic electroluminescent devices is characterized in that at least one of the luminescent compounds can form an organic luminescent layer through processes such as vacuum evaporation, spin coating, and inkjet printing.

[0037] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0038] (1) In a type of luminescent compound provided by the present invention, the methyl group at the 2-position or 3-position of anthracene can improve the solubility of the material, reduce the cost of material synthesis and purification, and can also reduce the aggregation between molecules, avoid fluorescence quenching caused by molecular stacking, and achieve high exciton utilization.

[0039] (2) A type of luminescent compound provided by the present invention, anthracene and The unit connection sites are twisted, which increases the molecular steric hindrance, reduces the charge transfer within the molecule, and can also reduce the aggregation between molecules, avoid fluorescence quenching caused by molecular accumulation, and achieve high exciton utilization;

[0040] (3) A type of luminescent compound provided by the present invention can be obtained by adjusting the Ar unit and The coupling sites, end groups, etc. of the molecules can be adjusted to adjust the emission spectrum, energy level, etc., and change the luminescence properties;

[0041] (4) A type of luminescent compound provided by the present invention, naphthalene, anthracene, Both are wide-bandgap units that can be used to construct blue fluorescent molecules that are currently in short supply, and both units have high fluorescence quantum yields and are expected to achieve high efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 is the cyclic voltammetry curve of compound M1;

[0043] Figure 2 is the photoluminescence spectrum of compound M1;

[0044] Figure 3 Solution processed organic light emitting diode device structures;

[0045] Figure 4 Electroluminescence spectra of solution-processed organic light-emitting diodes based on M2:v-DABNA as the emissive layer. DETAILED DESCRIPTION

[0046] The specific implementation of the present invention is further described below in conjunction with examples and drawings, but the implementation and protection of the present invention are not limited thereto. It should be noted that if there are processes that are not particularly described in detail below, they can be implemented or understood by those skilled in the art with reference to the prior art. If the manufacturer of the reagents or instruments used is not indicated, they are deemed to be conventional products that can be purchased commercially.

[0047] Example 1: Synthesis of Compound M1

[0048]

[0049] (1) Preparation of intermediate 1: Under nitrogen protection, 4-(naphthalene-2-)phenylboronic acid (1.98 g, 8 mmol), 9,10-dibromo-2-methylanthracene (2.80 g, 8 mmol), tetrakis(triphenylphosphine)palladium (92.5 mg, 1 mol%), 3 g potassium carbonate and 120 mL N,N-dimethylformamide were added to a 300 mL two-necked bottle, and heated to 100°C for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, repeatedly washed with deionized water, dissolved in dichloromethane, and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 3 g of a white solid with a yield of 79.2%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0050] (2) Preparation of compound M1: Under nitrogen protection, intermediate product 1 (3.00 g, 6.34 mmol), (9-phenyl-9H-carbazole-4-yl)boric acid (1.21 g, 4.22 mmol), tetrakis(triphenylphosphine)palladium (48.8 mg, 1 mol%), 2 g potassium carbonate and 80 mL N,N-dimethylformamide were added to a 300 mL two-necked bottle, and heated to 100°C for 12 hours. After the reaction was completed, the product was precipitated in methanol, filtered and collected, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2 g of a white solid with a yield of 74.5%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0051] Figure 1 is the cyclic voltammetry curve of compound M1, and the corresponding highest occupied molecular orbital (HOMO) energy level and lowest unoccupied molecular orbital (LUMO) energy level are -5.4 eV and -2.6 eV respectively;

[0052] Figure 2 This is the photoluminescence spectrum of compound M1. It can be found that the emission peak of the compound is around 430nm, which is a standard blue light emission.

[0053] Example 2: Preparation of Compound M2

[0054]

[0055] (1) Preparation of intermediate 2: Under nitrogen protection, 4-bromocarbazole (1.00 g, 4.06 mmol), 2 g potassium carbonate and 100 mL N,N-dimethylformamide were added to a 300 mL two-necked bottle, heated to 100 ° C and stirred vigorously for 1 hour, and then 3-iodobiphenyl (1.14 g, 4.06 mmol) and tetrakis(triphenylphosphine)palladium (47.0 mg, 1 mol%) were added, and the reaction was continued at 100 ° C for 10 hours. After the reaction was completed, the product was precipitated in methanol, filtered and collected, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 1.2 g of a white solid with a yield of 74.2%. 1 HNMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0056] (2) Preparation of intermediate product 3: Under nitrogen protection, intermediate product 2 (1.00 g, 2.51 mmol), pinacol diboron (0.64 g, 2.51 mmol), 0.5 g potassium acetate, 36.7 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 0.95 g of a white solid with a yield of 85.0%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0057] (3) Preparation of compound M2: Under nitrogen protection, add 2g of intermediate product 3 (4.49mmol), 2.13g of intermediate product 1 (4.49mmol), 104mg of tetrakis(triphenylphosphine)palladium (2mol%), N,N-dimethylformamide and 2g of potassium carbonate into a 300mL two-necked bottle. Heat to 100°C and react for 12 hours. After the reaction is completed, the product is precipitated in methanol, filtered and collected, repeatedly washed with deionized water, dissolved in dichloromethane, and dried over anhydrous sodium sulfate. The crude product is purified by column chromatography using petroleum ether as eluent to obtain 2.5g of white solid with a yield of 78.2%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0058] Example 3: Preparation of Compound M3

[0059]

[0060] (1) Preparation of intermediate 4: Under nitrogen protection, 1-bromodibenzothiophene (2.63 g, 10 mmol), biboronic acid pinacol ester (2.54 g, 10 mmol), 3.0 g potassium acetate, 146.3 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2 g of a white solid with a yield of 64.5%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0061] (2) Preparation of compound M3: Under nitrogen protection, 3.1 g of intermediate product 4 (10 mmol), 4.73 g of intermediate product 1 (10 mmol), 115.6 mg of tetrakis(triphenylphosphine)palladium (1 mol%), 100 mL of N,N-dimethylformamide and 4 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 4 g of a white solid with a yield of 69.3%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0062] Example 4: Preparation of Compound M4

[0063]

[0064] (1) Preparation of intermediate 5: Under nitrogen protection, 1-bromodibenzofuran (2.47 g, 10 mmol), biboronic acid pinacol ester (2.54 g, 10 mmol), 3.0 g potassium acetate, 146.3 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 1.9 g of a white solid with a yield of 64.6%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0065] (2) Preparation of compound M4: Under nitrogen protection, 2.9 g of intermediate product 5 (10 mmol), 4.73 g of intermediate product 1 (10 mmol), 115.6 mg of tetrakis(triphenylphosphine)palladium (1 mol%), 100 mL of N,N-dimethylformamide and 4 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 3.5 g of a white solid with a yield of 62.4%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0066] Example 5: Preparation of Compound M5

[0067]

[0068] (1) Preparation of intermediate product 6: Under nitrogen protection, 1-bromobenzo[1,2-b:4,5-b′]bisbenzofuran (3.37 g, 10 mmol), biboronic acid pinacol ester (2.54 g, 10 mmol), 3.0 g potassium acetate, 146.3 mg dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100° C. for 6 hours. The crude product was purified by column chromatography using petroleum ether as eluent to obtain 3.0 g of a white solid with a yield of 78.1%. 1 H NMR, 13 CNMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0069] (2) Preparation of compound M5: Under nitrogen protection, 3.84 g of intermediate product 6 (10 mmol), 4.73 g of intermediate product 1 (10 mmol), 115.6 mg of tetrakis(triphenylphosphine)palladium (1 mol%), 100 mL of N,N-dimethylformamide and 4 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, filtered and collected, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 4.2 g of a white solid with a yield of 64.5%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0070] Example 6: Preparation of Compound M6

[0071]

[0072] (1) Preparation of intermediate 7: Under nitrogen protection, 1-bromonaphtho[2,3-B]benzofuran (2.97 g, 10 mmol), biboronic acid pinacol ester (2.54 g, 10 mmol), 3.0 g potassium acetate, 146.3 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 3.0 g of a white solid with a yield of 87.2%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0073] (2) Preparation of compound M6: Under nitrogen protection, 3.44 g of intermediate product 7 (10 mmol), 4.73 g of intermediate product 1 (10 mmol), 115.6 mg of tetrakis(triphenylphosphine)palladium (1 mol%), 100 mL of N,N-dimethylformamide and 4 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 4.5 g of a white solid with a yield of 73.7%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0074] Example 7: Preparation of Compound M7

[0075]

[0076] (1) Preparation of intermediate product 8: Under nitrogen protection, 4-bromo-9,9-dimethylfluorene (2.73 g, 10 mmol), biboronic acid pinacol ester (2.54 g, 10 mmol), 3.0 g potassium acetate, 146.3 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2.8 g of a white solid with a yield of 87.4%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0077] (2) Preparation of compound M7: Under nitrogen protection, 3.2 g of intermediate product 8 (10 mmol), 4.73 g of intermediate product 1 (10 mmol), 115.6 mg of tetrakis(triphenylphosphine)palladium (1 mol%), 100 mL of N,N-dimethylformamide and 4 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 4.1 g of a white solid with a yield of 69.9%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0078] Example 8: Preparation of Compound M8

[0079]

[0080] (1) Preparation of intermediate product 9: Under nitrogen protection, 4-bromocarbazole (1.00 g, 4.06 mmol), 2 g potassium carbonate and 100 mL N,N-dimethylformamide were added to a 300 mL two-necked bottle, heated to 100 ° C and stirred vigorously for 1 hour, and then 2-iodonaphthalene (1.03 g, 4.06 mmol) and tetrakis(triphenylphosphine)palladium (47.0 mg, 1 mol%) were added, and the reaction was continued at 100 ° C for 10 hours. After the reaction was completed, the product was precipitated in methanol, filtered and collected, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 0.8 g of a white solid with a yield of 52.9%. 1 H NMR, 13 CNMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0081] (2) Preparation of intermediate 10: Under nitrogen protection, intermediate 9 (0.93 g, 2.51 mmol), pinacol diboron (0.64 g, 2.51 mmol), 0.5 g potassium acetate, 36.7 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 0.8 g of a white solid with a yield of 76.0%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0082] (3) Preparation of compound M8: Under nitrogen protection, 1.89 g of intermediate product 10 (4.49 mmol), 2.13 g of intermediate product 1 (4.49 mmol), 104 mg of tetrakis(triphenylphosphine)palladium (2 mol%), N,N-dimethylformamide and 2 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2.5 g of a white solid with a yield of 78.2%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0083] Example 9: Preparation of Compound M9

[0084]

[0085] (1) Preparation of intermediate 11: Under nitrogen protection, 4-bromocarbazole (1.00 g, 4.06 mmol), 2 g potassium carbonate and 100 mL N,N-dimethylformamide were added to a 300 mL two-necked bottle, heated to 100 ° C and stirred vigorously for 1 hour, and then 2-iodobiphenyl (1.14 g, 4.06 mmol) and tetrakis(triphenylphosphine)palladium (47.0 mg, 1 mol%) were added, and the reaction was continued at 100 ° C for 10 hours. After the reaction was completed, the product was precipitated in methanol, filtered and collected, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 1.3 g of a white solid with a yield of 76.5%. 1 HNMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0086] (2) Preparation of intermediate 12: Under nitrogen protection, intermediate 2 (1.00 g, 2.51 mmol), pinacol diboron (0.64 g, 2.51 mmol), 0.5 g potassium acetate, 36.7 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 0.96 g of a white solid with a yield of 85.3%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0087] (3) Preparation of compound M9: Under nitrogen protection, add 2g of intermediate product 12 (4.49mmol), 2.13g of intermediate product 1 (4.49mmol), 104mg of tetrakis(triphenylphosphine)palladium (2mol%), N,N-dimethylformamide and 2g of potassium carbonate into a 300mL two-necked bottle. Heat to 100°C and react for 12 hours. After the reaction is completed, the product is precipitated in methanol, filtered and collected, repeatedly washed with deionized water, dissolved in dichloromethane, and dried over anhydrous sodium sulfate. The crude product is purified by column chromatography using petroleum ether as eluent to obtain 2.6g of white solid with a yield of 78.6%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0088] Example 10: Preparation of Compound M10

[0089]

[0090] (1) Preparation of intermediate 13: Under nitrogen protection, 4-bromocarbazole (1.00 g, 4.06 mmol), 2 g potassium carbonate and 100 mL N,N-dimethylformamide were added to a 300 mL two-necked bottle, heated to 100 ° C and stirred vigorously for 1 hour, and then 1-iodo-3,5-diphenylbenzene (1.45 g, 4.06 mmol) and tetrakis(triphenylphosphine)palladium (47.0 mg, 1 mol%) were added, and the reaction was continued at 100 ° C for 10 hours. After the reaction was completed, the product was precipitated in methanol, filtered and collected, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 1.4 g of a white solid with a yield of 79.0%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0091] (2) Preparation of intermediate 14: Under nitrogen protection, intermediate 13 (1.19 g, 2.51 mmol), pinacol diboron (0.64 g, 2.51 mmol), 0.5 g potassium acetate, 36.7 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 1.1 g of a white solid with a yield of 84.0%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0092] (3) Preparation of compound M10: Under nitrogen protection, 2.34 g of intermediate product 14 (4.49 mmol), 2.13 g of intermediate product 1 (4.49 mmol), 104 mg of tetrakis(triphenylphosphine)palladium (2 mol%), N,N-dimethylformamide and 2 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2.9 g of a white solid with a yield of 82.0%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0093] Example 11: Preparation of Compound M11

[0094]

[0095] (1) Preparation of intermediate 15: Under nitrogen protection, 2.82 g 8-bromo-1-chlorodibenzo[b,d]furan (10 mmol), 1.22 g phenylboric acid (10 mmol), 231 mg tetrakis(triphenylphosphine)palladium (2 mol%), 100 mL N,N-dimethylformamide and 4 g potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2.2 g of a white solid with a yield of 66.9%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0096] (2) Preparation of intermediate 16: Under nitrogen protection, intermediate 15 (2.79 g, 10 mmol), pinacol diboron (2.54 g, 10 mmol), 3.0 g potassium acetate, 146 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 3.5 g of a white solid with a yield of 83.27%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0097] (3) Preparation of compound M11: Under nitrogen protection, 3.7 g of intermediate product 16 (10 mmol), 4.73 g of intermediate product 1 (10 mmol), 231 mg of tetrakis(triphenylphosphine)palladium (2 mol%), 100 mL of N,N-dimethylformamide and 4 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2.9 g of a white solid with a yield of 82.0%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0098] Example 12: Preparation of Compound M12

[0099]

[0100] (1) Preparation of intermediate 17: Under nitrogen protection, 2.82 g 8-bromo-1-chlorodibenzo[b,d]furan (10 mmol), 1.72 g 2-naphthaleneboric acid (10 mmol), 231 mg tetrakis(triphenylphosphine)palladium (2 mol%), 100 mL N,N-dimethylformamide and 4 g potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, repeatedly washed with deionized water, dissolved in dichloromethane, and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2.2 g of a white solid with a yield of 78.9%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0101] (2) Preparation of intermediate 18: Under nitrogen protection, intermediate 17 (3.29 g, 10 mmol), pinacol diboron (2.54 g, 10 mmol), 3.0 g potassium acetate, 146 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 3.2 g of a white solid with a yield of 76.13%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0102] (3) Preparation of compound M12: Under nitrogen protection, 4.20 g of intermediate product 18 (10 mmol), 4.73 g of intermediate product 1 (10 mmol), 231 mg of tetrakis(triphenylphosphine)palladium (2 mol%), 100 mL of N,N-dimethylformamide and 4 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2.9 g of a white solid with a yield of 82.0%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0103] Example 13: Preparation of Compound M13

[0104]

[0105] (1) Preparation of intermediate 19: Under nitrogen protection, 2.82 g 8-bromo-1-chlorodibenzo[b,d]furan (10 mmol), 2.12 g dibenzofuran-2-boric acid (10 mmol), 231 mg tetrakis(triphenylphosphine)palladium (2 mol%), 100 mL N,N-dimethylformamide and 4 g potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 2.5 g of a white solid with a yield of 67.8%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0106] (2) Preparation of intermediate product 20: Under nitrogen protection, intermediate product 19 (3.2 g, 10 mmol), bipyralidin (2.54 g, 10 mmol), 3.0 g potassium acetate, 146 mg dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium (2 mol%), and 100 mL 1,4-dioxane were placed in a 300 mL two-necked bottle. The mixture was heated at 100°C for 6 hours. The crude product was purified by column chromatography using petroleum ether as eluent to obtain 3.2 g of a white solid with a yield of 69.5%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0107] (3) Preparation of compound M13: Under nitrogen protection, 4.60 g of intermediate product 20 (10 mmol), 4.73 g of intermediate product 1 (10 mmol), 231 mg of tetrakis(triphenylphosphine)palladium (2 mol%), 100 mL of N,N-dimethylformamide and 4 g of potassium carbonate were added to a 300 mL two-necked bottle. The mixture was heated to 100°C and reacted for 12 hours. After the reaction was completed, the product was precipitated in methanol, collected by filtration, and repeatedly washed with deionized water. The product was dissolved in dichloromethane and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography using petroleum ether as the eluent to obtain 6 g of a white solid with a yield of 82.6%. 1 H NMR, 13 C NMR, MS and elemental analysis results showed that the obtained compound was the target product.

[0108] Embodiment 14

[0109] Preparation of organic light-emitting diodes by evaporation

[0110] Take the pre-made indium tin oxide (ITO) glass with a sheet resistance of 15Ω, clean it with acetone, detergent, deionized water and isopropanol ultrasonically, and treat it with plasma for 10 minutes. Then, in a vacuum evaporation device, 5nm thick 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) is sequentially evaporated on the ITO surface as a hole injection layer, 25nm thick 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC) is used as a hole transport layer, 15nm thick 4,4',4"-tri(carbazole-9-yl)triphenylamine (TCTA) is used as an exciton blocking layer, and luminescent compounds M1~M9 and blue light dopant (BD) materials are sequentially evaporated on the ITO surface. (CAS: 1252914-27-4) co-evaporation as the light-emitting layer, BD mass accounts for 2%, the thickness of the light-emitting layer is 20nm, 40nm thick 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) as the electron transport layer, 1nm thick lithium fluoride (LiF) as the electron injection layer, 100nm thick aluminum (Al) as the cathode. The device structure is: ITO / HATCN / TAPC / TCTA / M1~M9: BD (2%) / TPBi / LiF / Al.

[0111] The electroluminescence data of the prepared devices are listed in Table 1.

[0112] Table 1: Performance of evaporation-deposited organic light-emitting devices

[0113]

[0114] It can be found from Table 1 that the OLED devices prepared based on these compounds as the light-emitting layer have very low turn-on voltage, high brightness and current efficiency. According to the color coordinates, it can be found that these materials emit pure blue light.

[0115] Embodiment 15

[0116] Fabrication of Solution Processed Organic Light Emitting Diodes

[0117] Take the pre-made indium tin oxide (ITO) glass with a square resistance of 15Ω, clean it with acetone, detergent, deionized water and isopropanol ultrasonically, and treat it with plasma for 10 minutes. Spin-coat a polyethoxythiophene (PEDOT:PSS) film doped with polystyrene sulfonic acid on ITO with a thickness of 40nm. The PEDOT:PSS film is dried at 80℃ in a vacuum oven for 8 hours. Then, the hole transport material TFB-X is spin-coated on PEDOT:PSS with a thickness of 20nm, and heated to 200℃ in nitrogen for annealing and cross-linking. M2~M5, M10~M13 are respectively dissolved with v-DABNA (CAS: 2251782-13-3) in methyl benzoate solvent at a concentration of 15mg / mL, and the mass ratio of blue light dopant v-DABNA is 2%. The solution is spin-coated to obtain a light-emitting layer with a thickness of 40nm. A 30nm thick TPBi (CAS: 192198-85-9): LiQ (CAS: 850918-68-2) (3:7) layer was evaporated on the light-emitting layer as an electron transport layer. Finally, a 1nm thick Yb layer and a 100nm thick metal Ag layer were evaporated on the light-emitting layer in sequence. The device structure was ITO / PEDOT: PSS / TFB-X / light-emitting layer / TPBi: LiQ / Yb / Ag.

[0118] Figure 4 Electroluminescence spectrum of solution-processed organic light-emitting diode based on M2:v-DABNA as the light-emitting layer. The emission peak of the device is at 460nm, and the emission half-peak width is narrow, about 22nm, corresponding to the deep blue coordinates (0.13, 0, 10).

[0119] Table 2: Solution processed organic light emitting device performance

[0120]

[0121] It can be found from Table 2 that these compounds can be used as luminescent materials to prepare high-performance solution-processed blue light OLED devices.

[0122] The above embodiments are only preferred implementation modes of the present invention and are only used to explain the present invention rather than to limit the present invention. Any changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit of the present invention should fall within the scope of protection of the present invention.

Claims

1. A luminescent compound, characterized in that: Its chemical structure satisfies the following general formula: Wherein, X is O, S, NR, C-(R)2, wherein R is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms; Ar is a H atom or an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms; The unit is an aromatic hydrocarbon group having 12 to 60 carbon atoms or an aromatic heterocyclic group having 12 to 60 carbon atoms.

2. A luminescent compound according to claim 1, characterized in that Its chemical structure satisfies one of the following general formulas: Wherein, X is O, S, NR, C-(R)2, wherein R is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms; Ar is a H atom or an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms; The unit is an aromatic hydrocarbon group having 12 to 60 carbon atoms or an aromatic heterocyclic group having 12 to 60 carbon atoms.

3. A luminescent compound according to claim 1 or 2, characterized in that: The Ar is a H atom and one of the following structures:

4. A luminescent compound according to claim 1 or 2, characterized in that: The A unit is one of the following structures:

5. A luminescent compound according to claim 1, characterized in that Its chemical structure is one of the following:

6. A method for preparing the luminescent compound according to any one of claims 1 to 5, comprising the following steps: (1) 4-(2-naphthyl)phenylboronic acid and 9,10-dibromo-2-methylanthracene undergo a one-sided Suzuki coupling reaction to obtain compound 1; (2) Compound 1 and a boronic acid or boronic acid ester functional group The unit was subjected to a second Suzuki coupling to obtain the target compound.

7. The method for preparing the luminescent compound according to claim 6, characterized in that: In step (1), the reaction molar ratio of 4-(2-naphthyl)phenylboronic acid to 9,10-dibromo-2-methylanthracene is 0.2:1 to 2:1, the reaction temperature is 60 to 120° C., and the reaction time is 2 to 24 hours; In step (2), compound 1 and a boronic acid or boronic acid ester functional group are reacted The reaction molar ratio of the units is 1:1 to 1:2, the reaction temperature is 60 to 120° C., and the reaction time is 2 to 24 hours.

8. Use of a luminescent compound according to any one of claims 1 to 5 in an organic electroluminescent device, especially in a blue light emitting diode.

9. Use of a luminescent compound according to claim 8 in an organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a substrate, an anode layer, an organic layer and a cathode layer; The organic layer includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer; The organic light-emitting layer contains at least one of the light-emitting compounds according to any one of claims 1 to 5.

10. Use of the luminescent compound according to claim 8 in an organic electroluminescent device, characterized in that: The luminescent compound can form an organic luminescent layer by vacuum evaporation, spin coating or inkjet printing process.

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