Organic light-emitting material, organic electroluminescent device and optoelectronic device

Abstract

The present invention is applicable to the field of material technology and provides an organic light-emitting material, an organic electroluminescent device and a photoelectric device, wherein the organic light-emitting material is a heterocyclic organic electroluminescent compound containing nitrogen atoms, and the organic electroluminescent device prepared using the compound has the performance advantages of low driving voltage, high efficiency and long life. The present invention adopts a triazine functional group with strong electron-withdrawing ability to effectively improve the electron mobility of the electron transport material, improve the problem of electron-hole imbalance inside the organic electroluminescent device, and improve the luminous efficiency; secondly, a planar heteroaryl structure containing heteroatoms is introduced to further improve the electron mobility of the electron transport material. At the same time, the planar molecular structure can prevent the π-conjugated system of the core structure from being continued, ensuring a high triplet energy level and a wide band gap, further improving the luminous efficiency, and improving the degree of energy level matching of each layer of the device, reducing the driving voltage and extending the device life.

Description

Technical Field

[0001] The present invention belongs to the field of material technology, and in particular relates to an organic light-emitting material, an organic electroluminescent device and a photoelectric device. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a new and promising display technology that is gradually gaining popularity. OLEDs are electroluminescent devices formed by a multilayer organic thin film structure, where the organic thin film is a film of organic light-emitting material formed on a substrate using evaporation, deposition, or spin coating processes.

[0003] An organic electroluminescent element is a self-luminous element that utilizes the following principle: by applying an electric field, the fluorescent substance emits light by utilizing the recombination energy of holes injected from the anode and electrons injected from the cathode. It has the following structure: an anode, a cathode, and an organic material layer between the two. In order to improve the efficiency and stability of the organic electroluminescent element, the organic material layer generally includes multiple layers with different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer, an electron transport layer (ETL), and an electron injection layer (EIL). In this type of organic light-emitting element, when a voltage is applied between the anode and the cathode, holes from the anode and electrons from the cathode are injected into the organic material layer, and the generated excitons generate light with a specific wavelength when they migrate to the ground state. The structure of the electron transport materials currently used as electron transport layers usually contains nitrogen-containing heterocycles such as pyridine, pyrimidine, oxadiazole, triazole, imidazole, and electron-withdrawing groups such as phosphorus oxide, which have electron transport properties. As a key component of the OLED structure, the electron transport layer will also have a great impact on the life of the device. For example, the mobility and band structure of the material determine the local electric field, carrier and Joule heat distribution in the electron transport layer and its vicinity, thereby directly affecting the aging rate of organic materials and devices.

[0004] Although research on organic electroluminescent materials has been widely carried out in academia and industry, stable and efficient organic layer materials for organic electrical components have not yet been fully developed, and the industrialization process of this technology still faces many key issues. Summary of the Invention

[0005] The present invention provides an organic light-emitting material, aiming to solve the problems of poor stability and low light-emitting efficiency of existing organic light-emitting materials.

[0006] The present invention is achieved by providing an organic light-emitting material, characterized in that the structure of the organic light-emitting material is as shown in Formula 1:

[0007]

[0008] Wherein, said n is an integer of 0-4;

[0009] R1 to R4 are the same as or different from each other and are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic acid, sulfonyl, phosphate, phosphoryl, silicon, borane, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-30 membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-20 membered heteroaryl, substituted or unsubstituted 3-25 membered heteroarylamine, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryloxy;

[0010] The L is one of a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted 3-20 membered heteroarylene group;

[0011] Ar1 and Ar2 are one or more of a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted 3-30 membered heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-20 membered heteroaryl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C10-C30 fused ring group, and a substituted or unsubstituted C5-C30 spirocyclic group.

[0012] The present invention further provides an organic electroluminescent device, comprising a first electrode, a second electrode, and an organic layer located between the first electrode and the second electrode; the organic layer comprises the above-mentioned organic light-emitting material.

[0013] The present invention also provides a photoelectric device, which includes the organic electroluminescent device.

[0014] The compound of the present invention is specifically a nitrogen-containing heterocyclic organic electroluminescent compound. The organic electroluminescent device prepared using the compound has the performance advantages of low driving voltage, high efficiency, and long life. Specifically, the present invention adopts a triazine functional group with strong electron-withdrawing ability to effectively improve the electron mobility of the electron transport material, improve the problem of electron-hole imbalance inside the organic electroluminescent device, and improve the luminous efficiency; secondly, in addition to introducing triazine, a planar heteroaryl structure containing heteroatoms is introduced to further improve the electron mobility of the electron transport material. At the same time, the planar molecular structure can prevent the π-conjugated system of the core structure from being continued, ensuring a high triplet energy level (ET) and a wide band gap, further improving the luminous efficiency, and improving the degree of energy level matching between the device layers, reducing the driving voltage, and extending the device life. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a hydrogen nuclear magnetic resonance spectrum of the organic light-emitting material provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0016] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0017] In order to solve the problems of poor stability and low luminous efficiency of existing organic light-emitting materials, the present invention provides an organic light-emitting material as shown in Formula 1, specifically a heterocyclic organic electroluminescent compound containing nitrogen atoms, and the use of the compound to prepare an organic electroluminescent device has the performance advantages of low driving voltage, high efficiency and long life. Specifically, the present invention adopts a triazine functional group with strong electron-withdrawing ability to effectively improve the electron mobility of the electron transport material, improve the problem of electron-hole imbalance inside the organic electroluminescent device, and improve the luminous efficiency; secondly, in addition to introducing triazine, a planar heteroaryl structure containing heteroatoms is introduced to further improve the electron mobility of the electron transport material. At the same time, the planar molecular structure can prevent the π-conjugated system of the core structure from being continued, ensuring a high triplet energy level (ET) and a wide band gap, further improving the luminous efficiency, and improving the degree of energy level matching of each layer of the device, reducing the driving voltage and extending the life of the device.

[0018] Specifically, the present invention provides an organic light-emitting material, the structural formula of which is shown in Formula 1 below:

[0019]

[0020] In formula 1:

[0021] n is an integer selected from 0-4, preferably n=1;

[0022] R1 to R4 are the same as or different from each other and are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic acid, sulfonyl, phosphate, phosphoryl, silicon, borane; substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3-30 membered) heterocycloalkyl, wherein the heteroatom is selected from oxygen (O), nitrogen ( N), sulfur (S); substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (3-20 membered)heteroaryl, whose heteroatoms are selected from oxygen (O), nitrogen (N), and sulfur (S); substituted or unsubstituted (3-25 membered)heteroarylamino, whose heteroatoms are selected from oxygen (O), nitrogen (N), and sulfur (S); substituted or unsubstituted (C6-C60)arylamino, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C6-C60)aryloxy.

[0023] L is a linking bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (3-20-membered)heteroarylene group, wherein the heteroatom thereof is selected from oxygen (O), nitrogen (N), and sulfur (S).

[0024] Ar1 and Ar2 represent one or more of substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-30 membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-20 membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted (C6-C30)aryloxy, substituted or unsubstituted C10-C30 fused ring, substituted or unsubstituted C5-C30 spirocyclic group.

[0025] Preferably, R1 to R4 are the same as or different from each other and are each independently hydrogen, deuterium, halogen, cyano; substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C3-C10) cycloalkyl, substituted or unsubstituted (3-15-membered) heterocycloalkyl, whose heteroatoms are selected from oxygen (O), nitrogen (N), and sulfur (S); substituted or unsubstituted (C6-C25) aryl, substituted or unsubstituted (3-15-membered) heteroaryl, whose heteroatoms are selected from oxygen (O), nitrogen (N), and sulfur (S); substituted or unsubstituted (3-10-membered) heteroarylamino, whose heteroatoms are selected from oxygen (O), nitrogen (N), and sulfur (S); substituted or unsubstituted (C6-C30) arylamino, substituted or unsubstituted (C1-C15) alkoxy, and substituted or unsubstituted (C6-C20) aryloxy.

[0026] Preferably, Ar1 and Ar2 represent one or more of a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted 3- to 25-membered heterocycloalkyl group, wherein the heteroatom is N, O, S, Si, P, Se, etc.; a substituted or unsubstituted C6-C25 aryl group, a substituted or unsubstituted 3- to 18-membered heteroaryl group, wherein the heteroatom is N, O, S, Si, P, Se, etc.; a substituted or unsubstituted (C6-C20)aryloxy group, a substituted or unsubstituted C10-C20 fused ring group, and a substituted or unsubstituted C5-C20 spirocyclic group.

[0027] Preferably, said L represents

[0028]

[0029] Preferably, Ar1 and Ar2 represent

[0030]

[0031]

[0032] Then the above general formula 1, more preferably the general structural formula is:

[0033]

[0034] Wherein, R1 to R4, Ar1, Ar2 and L in the above general formulae 1-1 to 1-4 are as defined above.

[0035] In the above terms of the present invention, "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced by another substituent, and the position of substitution is not limited as long as the position is a position where the hydrogen atom is replaced (i.e., a position where a substituent can replace), and when two or more substituents are substituted, the two or more substituents can be the same or different from each other. 3- to 10-membered heteroaryl, wherein the heteroatom in the heteroaryl is selected from one or more of N, S, O, Si, P or Se, C1-C10 alkoxy, and C6-C20 arylamino.

[0036] In the above technical solution, it is further preferred that the organic light-emitting material (electron transport material) is any one of the following structures, but not limited thereto:

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] The electron transport material of the present invention can be prepared by a synthesis method known to those skilled in the art. Alternatively, the following reaction scheme is preferably used for preparation.

[0043] Synthesis Route 1:

[0044]

[0045] wherein R1 to R4, L, Ar1, Ar2, and n are as defined in the above chemical formula 1. Hal1 to Hal4 are selected from fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0046] In the above technical solution, the step 1 specifically includes the following steps:

[0047] Raw material B was dissolved in THF, then ventilated three times, cooled to -78°C, and n-BuLi was slowly added. The reaction was continued for 4 h. Raw material A was added under nitrogen protection, and the temperature was slowly raised to 25°C. The mixture was stirred for 12 h. Distilled water was then slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of DCM and PE (1:4) to obtain intermediate 1.

[0048] In the above technical solution, the step 2 specifically includes the following steps:

[0049] Intermediate 1 was dissolved in a dichloromethane solution, stirred evenly, cooled to 0°C, and boron trifluoride etherate was added dropwise. The reaction was allowed to react for 10 hours. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography using a mixed solution of DCM and PE (1:20) to obtain Intermediate 2.

[0050] In the above technical solution, step 3 specifically includes the following steps:

[0051] Dissolve intermediate 2 and raw material C in a mixed solution of toluene, ethanol and water, then ventilate 3 times, add potassium carbonate and palladium catalyst under nitrogen protection, stir evenly, heat to 90°C, and reflux for 6 hours; after the reaction is completed, lower the temperature slightly, filter with diatomaceous earth to remove salt and catalyst, cool the filtrate to room temperature, wash three times with water, retain the organic phase, and then extract the aqueous phase with ethyl acetate; after combining the organic phases, dry with anhydrous magnesium sulfate, and use a rotary evaporator to remove the solvent to obtain solid organic matter. Use a small amount of dichloromethane to completely dissolve the solid organic matter, then slowly add it dropwise to the petroleum ether solution, stir evenly, and precipitate is precipitated. Filter the solid, rinse with anhydrous ethanol and petroleum ether in turn, and dry to obtain intermediate 3;

[0052] In the above technical solution, step 4 specifically includes the following steps:

[0053] Intermediate 3 was dissolved in carbon tetrachloride solution, BPO was added, NBS was slowly added, and the mixture was stirred evenly. The temperature was slowly raised to 80°C and the reaction was carried out for 8 hours. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed from the reaction solution using a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V = 1:6) to obtain intermediate 4;

[0054] In the above technical solution, step 4 specifically includes the following steps:

[0055] Under nitrogen protection, intermediate 4 and raw material D were dissolved in toluene, ethanol and aqueous solution, cesium carbonate, phosphine ligand, and palladium catalyst were added, stirred evenly, heated to 90°C, and refluxed for 6 hours; after the reaction, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V = 4:1) to obtain Chemical Formula 1.

[0056] The present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer located between the first and second electrodes; in this case, the organic layer comprises at least one of a hole injection layer, a hole transport layer, a luminescence-assisting layer, a light-emitting layer, an electron transport layer, and an electron injection layer, and at least one of the above-mentioned compounds is contained in this organic layer. That is, the organic layer can be formed from a single compound represented by Formula 1 above or a mixture of two or more compounds. Preferably, the single compound represented by Formula 1 above or a mixture of two or more compounds can be contained in the electron transport layer.

[0057] The present invention does not limit the preparation method of the organic electroluminescent device, and conventional methods in the field can be used. The present invention preferably uses thin film evaporation, electron beam evaporation or physical vapor deposition to evaporate metal and conductive oxides and their alloys on the substrate to form an anode, and then forms an organic layer and evaporates the cathode thereon to obtain an organic electroluminescent device.

[0058] The present invention also provides a photoelectric device, which includes the organic electroluminescent device.

[0059] Specifically, the organic electroluminescent device can be applied to organic light emitting devices (OLEDs), organic solar cells (OSCs), electronic paper (e-paper), organic photoreceptors (OPCs), or organic thin film transistors (OTFTs).

[0060] The following are examples of certain embodiments of the present invention, which are not intended to limit the scope of the present invention.

[0061] In addition, it should be noted that the numerical values ​​given in the following examples are as accurate as possible, but those skilled in the art understand that due to unavoidable measurement errors and experimental operation problems, each number should be understood as an approximate number rather than an absolutely accurate value.

[0062] Example 1

[0063]

[0064] The raw material B-2 (40.00 mmol) was dissolved in 80.00 ml of THF solution, and then ventilated 3 times, cooled to -78 ° C, and n-BuLi (48.00 mmol) was slowly added. The reaction was continued for 4 hours. The raw material A-2 (48.00 mmol) was added under nitrogen protection, and the temperature was slowly raised to 25 ° C. and stirred for 12 hours. Then, distilled water was slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of DCM and PE (V: V = 1: 4) to obtain intermediate 1 (11.25 g, yield: 75.22%).

[0065] Intermediate 1 (29.44 mmol) was dissolved in 110.00 ml of dichloromethane solution, stirred evenly, cooled to 0°C, and boron trifluoride etherate (29.44 mmol) was added dropwise. The reaction was allowed to react for 10 h. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography using a mixed solution of DCM and PE (V:V = 1:20) to obtain intermediate 2 (8.52 g, yield 81.38%).

[0066] Intermediate 2 (22.49 mmol) and raw material C-2 (22.49 mmol) were dissolved in a mixed solution of 110.00 ml toluene, ethanol and water, and then ventilated three times. Potassium carbonate (44.98 mmol) and tetrakistriphenylphosphine palladium (0.22 mmol) were added under nitrogen protection, stirred evenly, heated to 90 ° C, and refluxed for 6 hours. After the reaction, the temperature was slightly lowered and filtered using diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water. The organic phase was retained and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried with anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator to obtain a solid organic matter. A small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to a petroleum ether solution and stirred evenly. A precipitate was precipitated and filtered to obtain a solid. The solid was washed with anhydrous ethanol and petroleum ether in turn and dried to obtain intermediate 3 (7.50 g, yield: 85.10%).

[0067] Intermediate 3 (17.86 mmol) was dissolved in 70.00 ml of carbon tetrachloride solution, BPO (0.18 mmol) was added, and NBS (35.72 mmol) was slowly added. The mixture was stirred evenly and the temperature was slowly raised to 80° C. for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed by a rotary evaporator. The remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=1:6) to obtain intermediate 4 (4.97 g, yield: 71.44%).

[0068] Under nitrogen protection, intermediate 4 (10.26 mmol) and raw material D-2 (10.26 mmol) were dissolved in 70.00 ml of toluene, ethanol and aqueous solution, and cesium carbonate (20.52 mmol), X-Phos (0.51 mmol), palladium acetate (0.51 mmol) were added, stirred evenly, heated to 90 ° C, and refluxed for 6 hours; after the reaction, the temperature was slightly lowered, and the mixture was filtered using diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V = 4:1) to obtain compound ET-2 (6.54 g, yield: 86.27%, Mw: 738.89).

[0069] The compound ET-2 prepared in Example 1 was tested and analyzed, and the results were as follows:

[0070] HPLC purity: >99.95%.

[0071] Mass spectrometry test: theoretical value is 738.89; tested value is 738.68.

[0072] Elemental analysis:

[0073] Calculated values: C, 87.78; H, 4.64; N, 7.58.

[0074] The test values ​​are: C, 87.49; H, 4.87; N, 7.76.

[0075] H NMR spectrum: Figure 1 shown.

[0076] Example 2

[0077]

[0078] The raw material B-36 (40.00 mmol) was dissolved in 80.00 ml of THF solution, and then ventilated 3 times, cooled to -78 ° C, and n-BuLi (48.00 mmol) was slowly added. The reaction was continued for 4 hours. The raw material A-36 (48.00 mmol) was added under nitrogen protection, and the temperature was slowly raised to 25 ° C. and stirred for 12 hours. Then, distilled water was slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of DCM and PE (1:4) to obtain intermediate 1 (11.23 g, yield: 75.08%).

[0079] Intermediate 1 (29.44 mmol) was dissolved in 110.00 ml of dichloromethane solution, stirred evenly, cooled to 0°C, and boron trifluoride etherate (29.44 mmol) was added dropwise. The reaction was allowed to react for 10 h. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography using a mixed solution of DCM and PE (1:20) to obtain intermediate 2 (8.51 g, yield 81.24%).

[0080] The intermediate 2 (22.49 mmol) and the raw material C-36 (22.49 mmol) were dissolved in a mixed solution of 110.00 ml of toluene, ethanol and water, and then ventilated three times. Potassium carbonate (44.98 mmol) and tetrakistriphenylphosphine palladium (0.22 mmol) were added under nitrogen protection, stirred evenly, heated to 90 ° C, and refluxed for 6 hours. After the reaction, the temperature was slightly lowered and filtered using diatomaceous earth to remove salts and catalysts. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. After the organic phases were combined, they were dried with anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator to obtain a solid organic matter. A small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to a petroleum ether solution and stirred evenly. A precipitate was precipitated and filtered to obtain a solid. It was washed with anhydrous ethanol and petroleum ether in turn and dried to obtain the intermediate 3 (7.48 g, yield: 84.88%).

[0081] Intermediate 3 (17.86 mmol) was dissolved in 70.00 ml of carbon tetrachloride solution, BPO (0.18 mmol) was added, and NBS (35.72 mmol) was slowly added. The mixture was stirred evenly and the temperature was slowly raised to 80° C. for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed by a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=1:6) to obtain intermediate 4 (5.01 g, yield: 72.03%).

[0082] Under nitrogen protection, intermediate 4 (12.82 mmol) and raw material D-36 (12.82 mmol) were dissolved in 80.00 ml of toluene, ethanol and aqueous solution, and cesium carbonate (25.64 mmol), X-Phos (0.64 mmol), palladium acetate (0.64 mmol) were added, stirred evenly, heated to 90 ° C, and refluxed for 6 hours; after the reaction, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V = 4:1) to obtain compound ET-36 (7.44 g, yield: 85.67%, Mw: 677.77).

[0083] The compound ET-36 prepared in Example 2 was tested and analyzed, and the results were as follows:

[0084] HPLC purity: >99.95%.

[0085] Mass spectrometry test: theoretical value is 677.77; tested value is 677.77.

[0086] Elemental analysis:

[0087] Calculated values: C, 83.29; H, 4.02; N, 10.33; O, 2.36.

[0088] The test values ​​are: C, 83.03; H, 4.25; N, 10.49; O, 2.57.

[0089] Example 3

[0090]

[0091] The raw material B-92 (40.00 mmol) was dissolved in 80.00 ml of THF solution, and then ventilated 3 times, cooled to -78 ° C, and n-BuLi (48.00 mmol) was slowly added. The reaction was continued for 4 hours. The raw material A-92 (48.00 mmol) was added under nitrogen protection, and the temperature was slowly raised to 25 ° C. and stirred for 12 hours. Then, distilled water was slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of DCM and PE (1:4) to obtain intermediate 1 (11.25 g, yield: 75.17%).

[0092] Intermediate 1 (29.44 mmol) was dissolved in 110.00 ml of dichloromethane solution, stirred evenly, cooled to 0°C, and boron trifluoride etherate (29.44 mmol) was added dropwise. The reaction was allowed to react for 10 h. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography using a mixed solution of DCM and PE (1:20) to obtain intermediate 2 (8.50 g, yield 81.19%).

[0093] The intermediate 2 (22.49 mmol) and the raw material C-92 (22.49 mmol) were dissolved in a mixed solution of 110.00 ml of toluene, ethanol and water, and then ventilated three times. Potassium carbonate (44.98 mmol) and tetrakistriphenylphosphine palladium (0.22 mmol) were added under nitrogen protection, stirred evenly, heated to 90 ° C, and refluxed for 6 hours. After the reaction, the temperature was slightly lowered and filtered using diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water. The organic phase was retained and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried with anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator to obtain a solid organic matter. A small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to a petroleum ether solution and stirred evenly. A precipitate was precipitated and filtered to obtain a solid. The solid was washed with anhydrous ethanol and petroleum ether in turn and dried to obtain the intermediate 3 (7.46 g, yield: 84.63%).

[0094] Intermediate 3 (17.86 mmol) was dissolved in 70.00 ml of carbon tetrachloride solution, BPO (0.18 mmol) was added, and NBS (35.72 mmol) was slowly added. The mixture was stirred evenly and the temperature was slowly raised to 80° C. for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed by a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=1:6) to obtain intermediate 4 (5.02 g, yield: 72.12%).

[0095] Under nitrogen protection, intermediate 4 (12.82 mmol) and raw material D-92 (12.82 mmol) were dissolved in 80.00 ml of toluene, ethanol and aqueous solution, and cesium carbonate (25.64 mmol), X-Phos (0.64 mmol), palladium acetate (0.64 mmol) were added, stirred evenly, heated to 90°C, and refluxed for 6 hours; after the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=4:1) to obtain compound ET-92 (7.65 g, yield: 82.77%, Mw: 792.94).

[0096] The compound ET-92 prepared in Example 3 was tested and analyzed, and the results were as follows:

[0097] HPLC purity: >99.95%.

[0098] Mass spectrometry test: theoretical value is 792.94; tested value is 792.77.

[0099] Elemental analysis:

[0100] Calculated values: C, 84.98; H, 4.61; F, 2.64; N, 7.77.

[0101] The test values ​​are: C, 84.72; H, 4.83; F, 2.79; N, 7.90.

[0102] Example 4

[0103]

[0104] The raw material B-142 (40.00 mmol) was dissolved in 80.00 ml of THF solution, and then ventilated 3 times, cooled to -78 ° C, and n-BuLi (48.00 mmol) was slowly added. The reaction was continued for 4 hours. The raw material A-142 (48.00 mmol) was added under nitrogen protection, and the temperature was slowly raised to 25 ° C. and stirred for 12 hours. Then, distilled water was slowly added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of DCM and PE (1:4) to obtain intermediate 1 (11.22 g, yield: 74.98%).

[0105] Intermediate 1 (29.44 mmol) was dissolved in 110.00 ml of dichloromethane solution, stirred evenly, cooled to 0°C, and boron trifluoride etherate (29.44 mmol) was added dropwise. The reaction was allowed to react for 10 h. After the reaction was completed, ethanol was added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM. The extracted organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography using a mixed solution of DCM and PE (1:20) to obtain intermediate 2 (8.50 g, yield 81.21%).

[0106] The intermediate 2 (22.49 mmol) and the raw material C-142 (22.49 mmol) were dissolved in a mixed solution of 110.00 ml of toluene, ethanol and water, and then ventilated three times. Potassium carbonate (44.98 mmol) and tetrakistriphenylphosphine palladium (0.22 mmol) were added under nitrogen protection, stirred evenly, heated to 90 ° C, and refluxed for 6 hours. After the reaction, the temperature was slightly lowered and filtered using diatomaceous earth to remove salts and catalysts. The filtrate was cooled to room temperature and washed three times with water. The organic phase was retained and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried with anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator to obtain a solid organic matter. A small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to a petroleum ether solution and stirred evenly. A precipitate was precipitated and filtered to obtain a solid. It was washed with anhydrous ethanol and petroleum ether in turn and dried to obtain the intermediate 3 (7.45 g, yield: 84.54%).

[0107] Intermediate 3 (17.86 mmol) was dissolved in 70.00 ml of carbon tetrachloride solution, BPO (0.18 mmol) was added, and NBS (35.72 mmol) was slowly added. The mixture was stirred evenly and the temperature was slowly raised to 80° C. for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed by a rotary evaporator. The remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=1:6) to obtain intermediate 4 (5.03 g, yield: 72.23%).

[0108] Under nitrogen protection, intermediate 4 (12.82 mmol) and raw material D-142 (12.82 mmol) were dissolved in 80.00 ml of toluene, ethanol and aqueous solution, and cesium carbonate (25.64 mmol), X-Phos (0.64 mmol), palladium acetate (0.64 mmol) were added, stirred evenly, heated to 90°C, and refluxed for 6 hours; after the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=4:1) to obtain compound ET-142 (7.81 g, yield: 79.66%, Mw: 764.89).

[0109] The compound ET-142 prepared in Example 4 was tested and analyzed, and the results were as follows:

[0110] HPLC purity: >99.95%.

[0111] Mass spectrometry test: theoretical value is 764.89; tested value is 764.73.

[0112] Elemental analysis:

[0113] Calculated values: C, 84.80; H, 4.22; N, 10.99.

[0114] The test values ​​are: C, 84.64; H, 4.47; N, 11.23.

[0115] Since the general structural formula is Formula 1 in the Summary of the Invention, the synthesis routes and principles of the other compounds are the same as those of the above-listed embodiments, so they are not listed here in detail. Among them, Examples 5 to 24 of the present invention can obtain the organic light-emitting materials shown in Table 1 below according to the above-mentioned preparation methods:

[0116] Table 1

[0117]

[0118]

[0119]

[0120]

[0121] In the organic electroluminescent device prepared using the organic light-emitting material provided in the above embodiment, when the organic layer includes an electron transport layer, the electron transport layer includes the organic light-emitting material provided in the above embodiment.

[0122] Device Example 1

[0123] The structure of the prepared OLED device is: ITO anode / HIL / HTL / EML / ETL / EIL / cathode / light extraction layer

[0124] a. ITO anode: the coating thickness is The ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate was cleaned twice in distilled water, ultrasonically washed for 30 minutes, and then repeatedly cleaned twice with distilled water, ultrasonically washed for 10 minutes. After washing, it was ultrasonically washed with methanol, acetone, and isopropanol in sequence (5 minutes each time), dried, and then transferred to a plasma cleaning machine for washing for 5 minutes. It was then sent to a vapor deposition machine, and the substrate was used as the anode, and other functional layers were evaporated on it in sequence.

[0125] b. HIL (hole injection layer): The hole injection layer materials HT-1 and P-dopant were vacuum-deposited at a deposition rate of 97:3, and the thickness was 10 nm.

[0126] c. HTL (hole transport layer): The evaporation rate is 130nm, and HT-1 is vacuum evaporated on the hole injection layer as a hole transport layer. The structure is shown below;

[0127] d. Luminous auxiliary layer: At a deposition rate of 10 nm, 10 nm of EBL-1 was vacuum-deposited on the hole transport layer as a light-emitting auxiliary layer.

[0128] e. EML (light-emitting layer): Then on the above-mentioned light-emitting auxiliary layer, At a deposition rate of 100 nm, a host material (Host) and a dopant material (Dopant) were vacuum-deposited to a thickness of 20 nm as the light-emitting layer. The chemical formulas of the Host and Dopant are shown below. The deposition rate ratio of the Host to Dopant was 98:2.

[0129] f. HBL (hole blocking layer): The evaporation rate is 5 nm, and HB-1 is vacuum-deposited on the light-emitting layer as a hole blocking layer. The structure is shown below:

[0130] g. ETL (Electron Transport Layer): The compound 2 provided in the above embodiment was vacuum-deposited at a deposition rate of 35 nm to serve as an electron transport layer.

[0131] h. EIL (electron injection layer): The evaporation rate is 1.0 nm, and a Yb film layer is evaporated to form an electron injection layer.

[0132] i. Cathode: The evaporation rate ratio is 1:9, and 18nm of magnesium and silver are evaporated, and the evaporation rate ratio is 1:9 to obtain an OLED device.

[0133] j. Light extraction layer: At a deposition rate of 100 nm, CPL-1 is vacuum-deposited on the cathode to a thickness of 70 nm as a light extraction layer. The substrate after deposition is then packaged. First, the cleaned cover is coated with UV glue using a coating device. The coated cover is then moved to the laminating section, where the deposited substrate is placed on top of the cover. Finally, the substrate and cover are bonded using a laminating device, and the UV glue is cured by light.

[0134]

[0135] Referring to the method provided in the above device embodiment 1, compounds 1, 13, 17, 18, 32, 36, 37, 51, 52, 54, 63, 74, 86, 90, 92, 142, 143, 147, 149, 150, 152, 157, and 157 were respectively selected to replace compound 2 to prepare corresponding organic electroluminescent devices, which are respectively recorded as device embodiments 2 to 24.

[0136] Device Comparison Example 1:

[0137] This comparative example provides an organic electroluminescent device. The only difference between the preparation method of this organic electroluminescent device and that of device example 1 is that this organic electroluminescent device uses existing comparative compounds a and b to replace the electron transport material (compound 2) in device example 1 for evaporation to prepare device comparative examples 1 and 2. The chemical structures of comparative compounds a and b are:

[0138]

[0139] The driving voltage, luminous efficiency, BI value and lifespan of the organic electroluminescent devices obtained from the device embodiments 1 to 19 and the device comparative examples 1 to 2 were characterized at a brightness of 1000 (nits). The test results are shown in Table 2 below.

[0140] Table 2

[0141]

[0142]

[0143] Note: In blue top-emitting devices, the current efficiency is greatly affected by chromaticity. Therefore, the influence of chromaticity on efficiency is taken into account, and the ratio of luminous efficiency to CIEy is defined as BI value, that is, BI = (cd / A) / CIEy.

[0144] As can be seen from Table 2, the luminous efficiency, BI and life of the organic electroluminescent device prepared using the compound of the present invention are significantly improved compared with the existing organic electroluminescent devices provided in Comparative Examples 1 and 2.

[0145] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An organic light-emitting material, characterized in that: The structure of the organic light-emitting material is shown in Formula 1: Wherein, said n is 1; The R1 to R4 are each independently hydrogen; The L is a connecting bond and one of the following groups: The Ar1 and Ar2 are one of the following groups:

2. The organic light-emitting material according to claim 1, wherein The structure of the organic light-emitting material is one of the following formulas 1-1, 1-2, 1-3, and 1-4:

3. The organic light-emitting material according to claim 1, wherein The organic light-emitting material is any one of the following structures:

4. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a first electrode, a second electrode, and an organic layer located between the first electrode and the second electrode; the organic layer comprises the organic light-emitting material according to any one of claims 1 to 3.

5. A photoelectric device, characterized in that: The optoelectronic device comprises the organic electroluminescent device according to claim 4.

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