A nitrogen-doped condensed ring resonance type organic compound and an organic electroluminescent device prepared therefrom

Abstract

The present invention discloses a nitrogen-doped condensed ring resonance type organic compound and an organic electroluminescent device prepared therefrom, belonging to the field of semiconductor technology. The structure of the organic compound of the present invention is shown in the general formula (1). The compound of the present invention has a narrow half-peak width, a high fluorescence quantum yield, and a suitable luminescent color. When used as a doping material in a luminescent layer material of an OLED luminescent device, it can be used as a green light doping material of the luminescent layer of the organic electroluminescent device, thereby improving the luminescent color purity of the device, improving the current efficiency and the device life.

Description

Technical Field

[0001] The invention relates to the field of semiconductor technology, and in particular to a nitrogen-doped condensed ring resonance type organic compound and an organic electroluminescent device prepared therefrom. Background Art

[0002] Traditional fluorescent doped materials are limited by early technologies and can only use 25% of singlet excitons formed by electrical excitation to emit light. The internal quantum efficiency of the device is low (up to 25%), and the external quantum efficiency is generally less than 5%, which is far behind the efficiency of phosphorescent devices. Since the strong spin-orbit coupling of the heavy atom center enhances intersystem crossing, phosphorescent materials can effectively use singlet and triplet excitons formed by electrical excitation to emit light, making the internal quantum efficiency of the device reach 100%. However, most phosphorescent materials are expensive, have poor material stability, poor color purity, and serious device efficiency roll-off, which limits their application in OLEDs.

[0003] With the advent of the 5G era, higher requirements are placed on color rendering standards. In addition to being efficient and stable, luminescent materials also require a narrower half-width to improve the purity of the device's luminescent color. Fluorescent doped materials can achieve high fluorescence quantum and narrow half-width through molecular engineering. Blue fluorescent doped materials have achieved a phased breakthrough, and the half-width of boron materials can be reduced to below 30nm. In the green light region, which is more sensitive to the human eye, research is mainly focused on phosphorescent doped materials, but their luminescent peak shape is difficult to narrow by simple methods. Therefore, in order to meet higher color rendering standards, it is of great significance to study efficient green fluorescent doped materials with narrow half-width.

[0004] In addition, TADF sensitized fluorescence technology (TSF) combines TADF materials with fluorescent doping materials, and uses TADF materials as exciton sensitization media to convert triplet excitons formed by electrical excitation into singlet excitons, and transfers energy to fluorescent doping materials through long-range energy transfer of singlet excitons. It can also achieve 100% device quantum efficiency. This technology can make up for the shortcomings of insufficient exciton utilization of fluorescent doping materials, and effectively give play to the characteristics of high fluorescence quantum yield, high device stability, high color purity and low price of fluorescent doping materials, and has broad prospects in OLEDs applications.

[0005] The use of phosphorescent sensitized devices can achieve further improvements in efficiency and life based on high-efficiency phosphorescent devices. In addition, due to the narrower emission half-width and narrow Stokes shift of the sensitized material itself, efficient energy transfer can be achieved while reducing the lifetime of excitons in the device, thereby significantly improving the device lifetime and achieving excellent color purity performance.

[0006] Nitrogen-doped condensed ring structures with resonance structures are more likely to achieve narrow half-width emission. Such materials are used in TADF-sensitized fluorescence technology and phosphorescence-sensitized devices to achieve high-efficiency, narrow half-width emission device preparation. Therefore, the development of TADF-sensitized fluorescence technology based on narrow half-width nitrogen-doped luminescent materials has unique advantages and strong potential in terms of BT.2020 display indicators. Summary of the invention

[0007] In view of the above problems existing in the prior art, the present invention provides a nitrogen-doped fused ring resonance type organic compound and an organic electroluminescent device prepared therefrom. The compound of the present invention has a narrow half-peak width and a high fluorescence quantum yield, and can be used as a green light doping material for the light-emitting layer of an organic electroluminescent device, thereby improving the luminescent color purity, efficiency and life of the device.

[0008] The technical solution of the present invention is as follows:

[0009] A nitrogen-doped fused ring resonance type organic compound, wherein the structure of the nitrogen-doped fused ring resonance type organic compound is shown in the general formula (1):

[0010]

[0011] In the general formula (1), Z represents C-R1; Z1 represents C or N;

[0012] R1 may be the same or different each time and may represent a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0013] M1 and M2 are independently substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 6-30 One of the cycloalkyl groups;

[0014] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C 1-10 Alkyl, C 1-10 Alkoxy, C 3-20 Cycloalkyl, C 6-30 Aryl, C 3-30 one or more of heteroaryl groups;

[0015] Adjacent R1 can also bond to form C 6-30 Aryl or C 6-30 Heteroaryl structures.

[0016] In a preferred embodiment, the structure of the organic compound is as shown in any one of the general formulas (2) to (11):

[0017]

[0018] In general formula (2) to general formula (11), Z has the same meaning as defined above;

[0019] X represents O, S, Se, N(R2), C(R3)(R4) or Si(R5)(R6);

[0020] R2 represents a substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0021] R3, R4, R5, and R6 are each independently a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0022] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C 1-10 Alkyl, C 1-10 Alkoxy, C 3-20 Cycloalkyl, C 6-30 Aryl, C 3-30 One or more heteroaryl groups.

[0023] In a preferred embodiment, the structure of the organic compound is as shown in any one of the general formulas (12) to (18):

[0024]

[0025] In the general formulae (12) to (18), Z and X have the same meanings as defined above.

[0026] In a preferred embodiment, the structure of the organic compound is as shown in any one of the general formulas (19) to (26):

[0027]

[0028] In general formula (19) to general formula (26), Z represents C-R1;

[0029] R1 may be the same or different each time and may represent a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0030] R a , R b , R c , R d , R e , R f Each occurrence of the same or different atoms may be a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0031] X represents O, S, Se, N(R2), C(R3)(R4) or Si(R5)(R6);

[0032] R2 represents a substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0033] R3, R4, R5, and R6 are each independently a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted C1-C 10Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0034] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C 1-10 Alkyl, C 1-10 Alkoxy, C 3-20 Cycloalkyl, C 6-30 Aryl, C 3-30 One or more heteroaryl groups.

[0035] In a preferred embodiment, each occurrence of R1 is the same or different and represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, an adamantyl group, a methyl group, a deuterated methyl group, a tritiated methyl group, a trifluoromethyl group, an ethyl group, a deuterated ethyl group, a tritiated ethyl group, an isopropyl group, a deuterated isopropyl group, a tritiated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a tritiated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a tritiated cyclopentyl group, a methyl-substituted cyclopentyl group , cyclohexyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenyl one of the following: carbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazine, phenyl-substituted boryl, methoxy, and tert-butoxy;

[0036] The R a , R b , R c , R d , R e , R fEach of the following is independently a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, an adamantyl group, a methyl group, a deuterated methyl group, a deuterated methyl group, a trifluoromethyl group, an ethyl group, a deuterated ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a deuterated cyclopentyl group, a methyl-substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated benzene group phenyl, diphenyl, deuterated diphenyl, tritiated diphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9, 9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy;

[0037] The R2 is represented by adamantyl, methyl, deuterated methyl, tritiated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritiated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated substituted biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spiro The invention can be selected from the group consisting of fluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, and tert-butoxy.

[0038] The R3-R6 are independently represented by methyl, ethyl, propyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, tert-butyl substituted phenyl, methyl One of substituted biphenyl, ethyl substituted biphenyl, isopropyl substituted biphenyl, tert-butyl substituted biphenyl, deuterated methyl substituted phenyl, deuterated ethyl substituted phenyl, deuterated isopropyl substituted phenyl, deuterated tert-butyl substituted phenyl, deuterated methyl substituted biphenyl, deuterated ethyl substituted biphenyl, deuterated isopropyl substituted biphenyl, deuterated tert-butyl substituted biphenyl, phenyl substituted amino, tert-butylbenzene substituted amino, tert-butyl substituted dibenzofuranyl, phenyl substituted tert-butyl, xanthone, phenyl substituted triazine;

[0039] The substituent for the substituent group may be selected from deuterium, methyl, tert-butyl, phenyl, biphenyl.

[0040] The specific structure of the nitrogen-doped fused ring resonance type organic compound is any one of the following structures:

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047] An organic electroluminescent device comprises a cathode and an anode, and an organic light-emitting functional layer therebetween. The organic light-emitting functional layer comprises a light-emitting layer, and the light-emitting layer contains the nitrogen-doped condensed ring resonance type organic compound.

[0048] In a preferred embodiment, the light-emitting layer comprises a main material and a doping material, and the doping material contains the nitrogen-doped condensed ring resonance type organic compound.

[0049] In a preferred embodiment, the light-emitting layer comprises a first main material, a second main material and a doping material, at least one of the first main material and the second main material is a TADF material, and the doping material is the nitrogen-doped condensed ring resonance type organic compound.

[0050] In a preferred embodiment, the light-emitting layer comprises a main material, an exciton-sensitizing material and a doping material, wherein the exciton-sensitizing material is a complex containing a metal element, and the doping material is the nitrogen-doped condensed ring resonance-type organic compound.

[0051] The beneficial technical effects of the present invention are:

[0052] (1) The compounds of the present invention are applied to OLED devices and can be used as doping materials for light-emitting layer materials. They can emit green fluorescence under the action of an electric field and can be applied to OLED lighting or OLED display fields;

[0053] (2) The compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%;

[0054] (3) The compound of the present invention is used as a doping material, and the TADF sensitizer is introduced as a second host, which can effectively improve the device efficiency;

[0055] (4) The compound of the present invention is used as a doping material, and a green phosphorescent material is introduced as a sensitizer, which can effectively improve the efficiency and life of the device;

[0056] (5) The spectral FWHM of the compound of the present invention is relatively narrow, which can effectively improve the color gamut of the device and the luminous efficiency of the device;

[0057] (6) The compound of the present invention does not contain boron, providing another green light narrow emission effect based on the synergistic resonance effect;

[0058] (7) The vapor deposition decomposition temperature of the compound of the present invention is relatively high, which can inhibit the vapor deposition decomposition of the material and effectively improve the device life. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in the present invention are applied;

[0060] Among them, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer.

[0061] Figure 2 Compound 11 in toluene solution (1×10 -5 M concentration) photoluminescence spectrum. DETAILED DESCRIPTION

[0062] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but they are not intended to limit the present invention.

[0063] The following examples are intended to better explain the present invention, but the scope of the present invention is not limited thereto.

[0064] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art;

[0065] Example 1 Synthesis of Compound 55:

[0066]

[0067] Add raw material A-1 (10.0 mmol) and 50 mL of glacial acetic acid to a three-necked flask in sequence, and use nitrogen protection, cool to 0°C using a low-temperature tank, add NBS (20.5 mmol) in batches, and stir at 0°C for 10 hours. Concentrate the reaction solution and purify it through a silica gel column using petroleum ether: ethyl acetate = 100:1 as a developing solvent to obtain intermediate a-1, LC-MS: measured value: 440.96 ([M+H] + ), theoretical value: 439.95.

[0068] Add intermediate a-1 (10 mmol) and 50 mL of anhydrous DMF to a three-necked flask in sequence, and use nitrogen protection. Add NaH (net content 12 mmol) wrapped in mineral oil (65%) in batches under ice-water bath conditions. Stir the mixture for 0.5 hours, and slowly drop the raw material B-1 (10 mmol) solution dissolved in 10 mL of anhydrous DMF. After the reaction is completed, add 100 mL of water to quench the reaction, and filter the large amount of white precipitate precipitated. Collect the precipitate and use dichloromethane solution, dry it with anhydrous sodium sulfate, filter it, concentrate the reaction solution and purify it through a silica gel column using petroleum ether: ethyl acetate = 500: 1 as a developing agent to obtain intermediate b-1. LC-MS: Measured value: 517.00 ([M+H] + ), theoretical value: 515.98.

[0069] The intermediate b-1 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, DMAc 50 mL were added to the two-necked flask in sequence, and then nitrogen protection was applied, and the mixture was heated under reflux and stirred for 12 hours. After cooling, the organic phase was separated and collected, and the organic phase was dried over anhydrous sodium sulfate, and then filtered and concentrated. The compound was separated by a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain the intermediate c-1. LC-MS: Measured value: 437.11 ([M+H] + ), theoretical value: 436.06.

[0070] Under nitrogen protection, 10 mmol of intermediate c-1, 20 mmol of raw material C-1 (excess to ensure the reaction), 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 70 mL of dichlorobenzene were added to a three-necked flask and refluxed for 20 hours. After the reaction was completed, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate d-1. LC-MS: Measured value: 613.23 ([M+H] + ), theoretical value: 612.12. 1 HNMR (400 MHz, deuterated chloroform) δ8.33 (dd, 1H), 8.15 (dd, 1H), 8.02 (dd, 1H), 7.98 (d, 1H), 7.93 (dd, 1H), 7.89-7.82 (m, 2H), 7.78 (d, 1H), 7.74 (dd, 1H), 7.65-7.59 (m, 3H), 7.55 (d, 1H), 7.39-7.33 (m, 5H), 7.13-7.05 (m, 1H), 2.33-2.24 (m, 6H).

[0071] To a sealed pressure tube, add intermediate d-1 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, and DMAc 50 mL in sequence, followed by nitrogen protection, heating under reflux and stirring for 48 hours. After cooling, separate the liquids and collect the organic phase. The organic phase is dried over anhydrous sodium sulfate, then filtered and concentrated, and the compound is separated by passing through a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain compound 55. 1 HNMR (400 MHz, deuterated chloroform) δ8.89 (dd, 1H), 8.62 (dd, 1H), 8.22 (dd, 1H), 7.97-7.93 (m, 2H), 7.85-7.82 (m, 1H), 7.79 (t, 1H), 7.69-7.60 (m, 2H), 7.58 (dd, 1H), 7.55 (m, 1H), 7.49-7.42 (m, 2H), 7.33-7.18 (m, 5H), 2.24 (m, 6H).

[0072] Example 2 Synthesis of Compound 70:

[0073]

[0074] Under nitrogen protection, 10 mmol of intermediate c-1, 20 mmol of raw material A-2 (excessive to ensure the reaction), 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 70 mL of dichlorobenzene were added to a three-necked flask and refluxed for 12 hours. After the reaction was completed, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate a-2. LC-MS: Measured value: 645.13 ([M+H] + ), theoretical value: 644.09. 1 HNMR (400 MHz, deuterated chloroform) δ8.22 (dd, 1H), 8.04 (dd, 1H), 7.98-7.92 (m, 2H), 7.87 (dd, 1H), 7.75 (dd, 1H), 7.69-7.65 (m, 2H), 7.62 (d, 1H), 7.59-7.55 (m, 4H), 7.34-7.28 (m, 5H), 7.25-7.11 (m, 1H), 2.13-2.34 (m, 6H).

[0075] To a sealed pressure tube, add intermediate a-2 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, and DMAc 50 mL in sequence, followed by nitrogen protection, heating under reflux and stirring for 18 hours, cooling, separating and collecting the organic phase, drying the organic phase over anhydrous sodium sulfate, then filtering and concentrating the organic phase, and separating the compound through a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain compound 70. 1 HNMR (400 MHz, deuterated chloroform) δ8.72 (dd, 1H), 8.33 (dd, 1H), 8.03 (m, 1H), 7.92 (m, 1H), 7.66-7.56 (m, 2H), 7.49-7.43 (m, 2H), 7.40 (d, 1H), 7.38-7.15 (m, 9H), 2.28 (d, 6H).

[0076] Example 3 Synthesis of Compound 85:

[0077]

[0078] Under nitrogen protection, 10 mmol of intermediate c-1, 20 mmol of raw material A-3 (excess amount to ensure the reaction), 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 20 mL of dichlorobenzene were added to a sealed pressure-resistant tube and heated by microwave for 6 hours. After the reaction, the organic layer was decompressed and concentrated, and then purified by silica gel column chromatography to obtain compound 85. 1 HNMR (400 MHz, deuterated chloroform) δ8.44 (d, 1H), 8.15 (dd, 1H), 8.02 (d, 1H), 7.97-7.88 (m, 3H), 7.72 (dd, 1H), 7.68 (dd, 1H), 7.49-7.33 (m, 7H), 2.51-2.47 (m, 6H), 2.35 (s, 9H), 2.08 (s, 9H).

[0079] Example 4 Synthesis of Compound 120:

[0080]

[0081]

[0082] Add raw material A-4 (10mmol) and 50mL anhydrous DMF to a three-necked flask in sequence, and use nitrogen protection. Add NaH (net content 12mmol) wrapped in mineral oil (65%) in batches under ice-water bath conditions. Stir the mixture for 0.5 hours, and slowly drop the raw material B-4 (10mmol) solution dissolved in 10mL anhydrous DMF. After the reaction is completed, add 100mL of water to quench the reaction, and filter the large amount of white precipitate precipitated. Collect the precipitate and use dichloromethane solution, dry it with anhydrous sodium sulfate, filter it, concentrate the reaction solution and purify it through a silica gel column using petroleum ether: ethyl acetate = 500: 1 developing agent to obtain intermediate a-4. LC-MS: Measured value: 428.14 ([M+H] + ), theoretical value: 427.09.

[0083] Add intermediate a-1 (10 mmol) and 50 mL of anhydrous DMF to a three-necked flask in turn, and use nitrogen protection. Add NaH (net content 12 mmol) wrapped in mineral oil (65%) in batches under ice-water bath conditions. Stir the mixture for 1 hour, and slowly drop the raw material C-4 (10 mmol) solution dissolved in 10 mL of anhydrous DMF. After the reaction is completed, add 100 mL of water to quench the reaction, and filter the large amount of white precipitate precipitated. Collect the precipitate and use dichloromethane solution, dry it with anhydrous sodium sulfate, filter it, concentrate the reaction solution and purify it through a silica gel column using petroleum ether: ethyl acetate = 500: 1 as a developing agent to obtain intermediate b-4. LC-MS: Measured value: 573.03 ([M+H] + ), theoretical value: 572.05.

[0084] The intermediate b-4 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, DMAc 50 mL were added to the two-necked flask in sequence, and then nitrogen protection was applied, and the mixture was heated under reflux and stirred for 17 hours. After cooling, the organic phase was separated and collected, and the organic phase was dried over anhydrous sodium sulfate, and then filtered and concentrated. The compound was separated by a silica gel column with petroleum ether: ethyl acetate = 100: 1 as the developing solvent to obtain the intermediate c-4. LC-MS: Measured value: 493.10 ([M+H] + ), theoretical value: 492.12.

[0085] Under nitrogen protection, 10 mmol of intermediate c-4, 20 mmol of intermediate a-4 (excess to ensure the reaction), 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 70 mL of dichlorobenzene were added to a three-necked flask and refluxed for 10 hours. After the reaction was completed, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate d-4. LC-MS: Measured value: 840.31 ([M+H] + ), theoretical value: 839.29. 1 HNMR (400 MHz, deuterated chloroform) δ7.92 (dd, 1H), 7.79 (dd, 2H), 7.77-7.71 (m, 2H), 7.66-7.58 (m, 2H), 7.51-7.35 (m, 13H), 7.31-7.12 (m, 2H), 2.43-2.37 (m, 6H), 1.49 (d, 18H).

[0086] To a sealed pressure tube were added intermediate d-4 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, and DMAc 50 mL, followed by nitrogen protection, heating under reflux and stirring for 22 hours. After cooling, the liquids were separated and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, then filtered and concentrated, and the compound was separated by passing through a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain compound 120. 1 HNMR (400 MHz, deuterated chloroform) δ8.28 (s, 1H), 8.13 (dd, 1H), 8.05 (dd, 1H), 7.99 (dd, 1H), 7.97-7.88 (m, 3H), 7.56-7.48 (m, 2H), 7.46-7.39 (m, 6H), 7.33-7.28 (m, 3H), 7.26-7.19 (m, 3H), 2.51 (s, 6H), 1.49 (d, 18H).

[0087] Example 5 Synthesis of Compound 141:

[0088]

[0089] Under nitrogen protection, 10 mmol of raw material A-5, 10 mmol of raw material B-5, 20 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, 50 mL of tetrahydrofuran and 5 mL of water were added to a three-necked flask and refluxed for 8 hours. After the reaction was completed, the organic phase was separated and collected, the organic layer was concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain intermediate a-5. LC-MS: Measured value: 439.16 ([M+H] +), theoretical value: 438.10.

[0090] Under nitrogen protection, 10 mmol of intermediate c-4, 20 mmol of intermediate a-5 (excess to ensure the reaction), 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 70 mL of dichlorobenzene were added to a three-necked flask and refluxed for 16 hours. After the reaction was completed, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-5. LC-MS: Measured value: 851.34 ([M+H] + ), theoretical value: 850.29. 1 HNMR (400 MHz, deuterated chloroform) δ8.72 (s, 1H), 8.39 (dd, 1H), 8.27 (s, 1H), 8.16 (dd, 1H), 8.03 (dd, 1H), 7.97 (d, 1H), 7.92 (m, 1H), 7.88 (d, 1H), 7.68 (dd, 1H), 7.64-7.58 (m, 5H), 7.56-7.49 (m, 5H), 7.41-7.25 (m, 2H), 7.09 (d, 1H), 7.03 (m, 1H), 2.29-2.24 (m, 6H), 1.25 (d, 18H).

[0091] To a sealed pressure tube were added intermediate b-5 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, and DMAc 50 mL, followed by nitrogen protection, heating under reflux and stirring for 21 hours. After cooling, the liquids were separated and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, then filtered and concentrated, and the compound was separated by a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain compound 141. 1 HNMR (400 MHz, deuterated chloroform) δ8.39 (s, 1H), 8.15-8.05 (m, 2H), 7.92 (dd, 1H), 7.84-7.79 (m, 3H), 7.73-7.66 (m, 2H), 7.57-7.46 (m, 7H), 7.43 (dd, 1H), 7.37-7.18 (m, 5H), 2.36 (s, 6H), 1.41 (d, 18H).

[0092] Example 6 Synthesis of Compound 152:

[0093]

[0094]

[0095] Add raw material A-6 (10.0 mmol) and 50 mL of glacial acetic acid to the three-necked flask in sequence, and use nitrogen protection, cool to 0 ° C using a low temperature tank, add NBS (20.5 mmol) in batches, and stir at 0 ° C for 3 hours. Concentrate the reaction solution and purify it through a silica gel column using petroleum ether: ethyl acetate = 100: 1 as a developing solvent to obtain intermediate a-6, LC-MS: Measured value: 525.10 ([M+H] + ), theoretical value: 524.05.

[0096] Add intermediate a-6 (10mmol) and 50mL anhydrous DMF to a three-necked flask in sequence, and use nitrogen protection. Add NaH (net content 12mmol) wrapped in mineral oil (65%) in batches under ice-water bath conditions. Stir the mixture for 45 minutes, and slowly drop the raw material B-6 (10mmol) solution dissolved in 10mL anhydrous DMF. After the reaction is completed, add 100mL of water to quench the reaction, and filter the large amount of white precipitate precipitated. Collect the precipitate and use dichloromethane solution, dry it with anhydrous sodium sulfate, filter it, concentrate the reaction solution and purify it through a silica gel column using petroleum ether: ethyl acetate = 500: 1 developing agent to obtain intermediate b-6. LC-MS: Measured value: 657.18 ([M+H] + ), theoretical value: 656.14.

[0097] The intermediate b-6 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, DMAc 50 mL were added to the two-necked flask in sequence, and then nitrogen protection was applied, and the mixture was heated under reflux and stirred for 12 hours. After cooling, the organic phase was separated and collected, and the organic phase was dried over anhydrous sodium sulfate, and then filtered and concentrated. The compound was separated by a silica gel column with petroleum ether: ethyl acetate = 100: 1 as the developing solvent to obtain the intermediate c-6. LC-MS: Measured value: 577.29 ([M+H] + ), theoretical value: 576.21.

[0098] Under nitrogen protection, 10 mmol of intermediate c-6, 20 mmol of raw material C-6 (excess to ensure the reaction), 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 70 mL of dichlorobenzene were added to a three-necked flask and refluxed for 18 hours. After the reaction was completed, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate d-6. LC-MS: Measured value: 833.40 ([M+H] + ), theoretical value: 832.34. 1HNMR (400 MHz, deuterated chloroform) δ8.28-8.19 (m, 2H), 8.12-8.00 (m, 2H), 7.83-7.76 (m, 3H), 7.71 (m, 1H), 7.62-7.50 (m, 5H), 7.45-7.21 (m, 3H), 7.13 (d, 1H), 1.60–1.49 (m, 27H), 1.45 (s, 9H).

[0099] To a sealed pressure tube were added intermediate d-6 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, and DMAc 50 mL, followed by nitrogen protection, heating under reflux and stirring for 41 hours. After cooling, the liquids were separated and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, then filtered and concentrated, and the compound was separated by a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain compound 152. 1 HNMR (400 MHz, deuterated chloroform) δ8.48-8.37 (m, 4H), 8.25-8.12 (m, 1H), 8.01 (m, 1H), 7.83-7.59 (m, 3H), 7.42 (m, 4H), 7.30-7.11 (m, 3H), 1.50-1.46 (m, 27H), 1.44 (s, 9H).

[0100] Example 7 Synthesis of Compound 172:

[0101]

[0102]

[0103] Under nitrogen protection, the raw material D-1 (17.8mmol) was dissolved in anhydrous THF (400mL), the reaction system was cooled to 0°C, and a solution of concentrated hydrochloric acid (81.7mL) in water (235mL) was slowly added dropwise. After the addition was complete, a solution of NaNO2 (26.7mmol) in water (90mL) was slowly added dropwise, and the reaction temperature was kept below 5°C. After the addition was complete, the reaction system continued to stir for 15 minutes. A solution of KI (35.5mmol) in water (371.5mL) was added dropwise to the reaction system, and the reaction temperature was kept below 5°C. After the addition was complete, the temperature was maintained and stirred for 2h. The reaction was then quenched with a saturated sodium sulfite solution, extracted with ethyl acetate and washed with saturated brine in turn, dried over anhydrous Na2SO4, the solvent was spin-dried, and column chromatography gave the raw material A-7. LC-MS: Measured value: 393.17 ([M+H] + ), theoretical value: 392.10.

[0104] Under nitrogen protection, 10 mmol of raw material A-4, 10 mmol of raw material A-7, 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 70 mL of dichlorobenzene were added to a three-necked flask and refluxed for 14 hours. After the reaction was completed, the organic layer was decompressed and concentrated, and then purified by silica gel column chromatography to obtain intermediate a-7. LC-MS: Measured value: 560.23 ([M+H] + ), theoretical value: 559.19.

[0105] Under nitrogen protection, 10 mmol of intermediate c-6, 20 mmol of intermediate a-7 (excess to ensure the reaction), 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 70 mL of dichlorobenzene were added to a three-necked flask and refluxed for 13 hours. After the reaction was completed, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-7. LC-MS: Measured value: 1056.52 ([M+H] + ), theoretical value: 1055.48. 1 HNMR (400 MHz, deuterated chloroform) δ8.42-8.33 (m, 2H), 8.26 (m, 1H), 8.17-7.95 (m, 1H), 7.89 (d, 1H), 7.60-7.18 (m, 20H), 1.45-1.30 (m, 45H).

[0106] To a sealed pressure tube were added intermediate b-7 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, and DMAc 50 mL, followed by nitrogen protection, heating under reflux and stirring for 44 hours. After cooling, the liquids were separated and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, then filtered and concentrated, and the compound was separated by passing through a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain compound 172. 1 HNMR (400 MHz, deuterated chloroform) δ8.63 (s, 1H), 8.55 (m, 1H), 8.46-8.25 (m, 3H), 8.11-7.99 (m, 1H), 7.93-7.82 (m, 1H), 7.79-7.64 (m, 3H), 7.59-7.55 (m, 3H), 7.45-7.16 (m, 11H), 1.49 (d, 18H), 1.45-1.41 (m, 27H).

[0107] Example 8 Synthesis of Compound 183:

[0108]

[0109] Under nitrogen protection, 10 mmol of intermediate c-6, 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 20 mL of dichlorobenzene were added to a sealed pressure tube and heated by microwave for 60 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 183. 1 HNMR (400 MHz, deuterated chloroform) δ8.25 (d, 2H), 8.15 (d, 2H), 7.83-7.75 (m, 4H), 7.43 (m, 4H), 7.18 (dd, 2H), 7.12 (t, 4H), 1.49 (d, 36H), 1.44 (s, 18H).

[0110] Example 9 Synthesis of Compound 11:

[0111]

[0112] Add raw material A-5 (10mmol) and 50mL anhydrous DMF to a three-necked flask in sequence, and use nitrogen protection. Add NaH (net content 12mmol) wrapped in mineral oil (65%) in batches under ice-water bath conditions. The mixture is stirred for 0.5 hours, and the raw material B-1 (10mmol) solution dissolved in 10mL anhydrous DMF is slowly added dropwise. After the reaction is completed, 100mL of water is added to quench the reaction, and a large amount of white precipitate is filtered. The precipitate is collected and filtered with a dichloromethane solution, dried over anhydrous sodium sulfate, and then the reaction solution is concentrated and purified by a silica gel column using petroleum ether: ethyl acetate = 500: 1 as a developing agent to obtain intermediate b-8. LC-MS: Measured value: 488.11 ([M+H] + ), theoretical value: 487.95.

[0113] The intermediate b-8 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, DMAc 50 mL were added to the two-necked flask in sequence, and then nitrogen protection was applied, and the mixture was heated under reflux and stirred for 11 hours. After cooling, the organic phase was separated and collected, and the organic phase was dried over anhydrous sodium sulfate, and then filtered and concentrated. The compound was separated by a silica gel column with petroleum ether: ethyl acetate = 100: 1 as the developing solvent to obtain the intermediate c-7. LC-MS: Measured value: 409.15 ([M+H] + ), theoretical value: 408.03.

[0114] Under nitrogen protection, 10 mmol of intermediate c-7, 20 mmol of raw material C-7 (excessive to ensure the reaction), 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6 and 70 mL of dichlorobenzene were added to a three-necked flask and refluxed for 13 hours. After the reaction was completed, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate d-7. LC-MS: Measured value: 535.13 ([M+H] + ), theoretical value: 534.07.

[0115] The intermediate d-7 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, DMAc 50 mL were added to the sealed pressure tube in sequence, and then nitrogen protection was applied, and the mixture was heated under reflux and stirred for 23 hours. After cooling, the organic phase was separated and collected, and the organic phase was dried over anhydrous sodium sulfate, and then filtered and concentrated. The compound was separated by a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain compound 11. Compound 11 was dissolved in a toluene solution (1×10 -5 M) is shown in the attached Figure 2 .according to Figure 2 It can be seen that the peak value of compound 11 in toluene solution is 540 nm and the half-peak width is 26 nm.

[0116] The structural characteristics of the compounds obtained in each example are shown in Table 1

[0117] Table 1

[0118]

[0119]

[0120] The compounds of the present invention are used in light-emitting devices and can be used as doping materials for light-emitting layers. The physical and chemical properties of the compounds prepared in the above embodiments of the present invention were tested, and the test results are shown in Table 2:

[0121] Table 2

[0122]

[0123] Note: PLQY (fluorescence quantum yield) and FWHM (half-maximum width) are measured in thin film state by Horiba's Fluorolog-3 series fluorescence spectrometer.

[0124] It can be seen from the data in the above table that the compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%; at the same time, the spectral FWHM of the material is narrow, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device; finally, the evaporation decomposition temperature of the material is high, which can inhibit the evaporation decomposition of the material and effectively improve the life of the device.

[0125] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device examples 1-9 and device comparison examples 1-3. The device manufacturing process of device examples 2-9 and device comparison examples 1-3 of the present invention is exactly the same as that of device example 1, and the same substrate material and electrode material are used. The film thickness of the electrode material is also the same. The difference is that the light-emitting layer material in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 3-1 and Table 4 respectively.

[0126] Device Example 1

[0127] like Figure 1 As shown, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washing with a cleaning agent (SemicleanM-L20), washing with pure water, drying, and then ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as a hole injection layer 3, and the mass ratio of HT-1 and HI-1 is 97:3. Then evaporate HT-1 with a thickness of 60nm as a hole transport layer 4. Then evaporate EB-1 with a thickness of 30nm as an electron blocking layer 5. After the above electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is prepared, using GH-1 and GH-2 as the main materials, compound 55 as the doping material, GH-1, GH-2 and compound 55 The mass ratio is 69:30:1, and the film thickness of the light-emitting layer is 30nm. After the above-mentioned light-emitting layer 6, HB-1 was vacuum-deposited to a thickness of 5 nm, which was the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq were vacuum-deposited to a thickness of 30 nm, with a mass ratio of ET-1 to Liq of 1:1. On the electron transport layer 8, a LiF layer with a thickness of 1 nm was made by vacuum evaporation, which was the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a thickness of 80 nm was made by vacuum evaporation, with a mass ratio of Mg to Ag of 1:9, which was used as the cathode layer 10.

[0128] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device embodiments 10-18 and device comparative examples 4-6. The device manufacturing process of device embodiments 11-18 of the present invention and device comparative examples 4-6 is exactly the same as that of device embodiment 10, and the same substrate material and electrode material are used. The film thickness of the electrode material is also the same. The difference is that the light-emitting layer material in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 3-2 and Table 4 respectively.

[0129] Device Example 10

[0130] The transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washed with a cleaning agent (SemicleanM-L20), washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as the hole injection layer 3, and the mass ratio of HT-1 to HI-1 is 97:3. Then, HT-1 with a thickness of 60nm is evaporated as the hole transport layer 4. Then, EB-1 with a thickness of 30nm is evaporated as the electron blocking layer 5. After the above-mentioned electron blocking material is deposited, the light-emitting layer 6 of the OLED light-emitting device is prepared, using GH-1 and GH-2 as the main materials, GD-1 as the first doping material, and compound 55 as the second doping material. The mass ratio of GH-1, GH-2, GD-1 and compound 55 is 66:30:3:1, and the thickness of the light-emitting layer is 30nm. After the above-mentioned light-emitting layer 6, HB-1 is vacuum-deposited with a film thickness of 5nm. This layer is the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq are vacuum-deposited. The mass ratio of ET-1 and Liq is 1:1, and the film thickness is 30nm. This layer is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1nm is prepared by a vacuum evaporation device. This layer is the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a film thickness of 80nm is prepared by a vacuum evaporation device. The mass ratio of Mg and Ag is 1:9. This layer is used as the cathode layer 10.

[0131] The molecular structure formula of the relevant materials is shown below:

[0132]

[0133] After the OLED light-emitting device is completed as described above, the anode and cathode are connected by a known driving circuit, and the operating voltage, current efficiency and life of the device are measured. Device Examples 10-18 and Comparative Examples 4-6 prepared by the same method are shown in Table 3-2; the test results of the voltage, current efficiency and life of the obtained device are shown in Table 4.

[0134] Table 3-1

[0135]

[0136]

[0137] Table 3-2

[0138]

[0139] Table 4

[0140]

[0141]

[0142] Note: Voltage, current efficiency, and luminous peak are measured using IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.); the life test system is EAS-62C OLED device life tester from Japan System Technology Co., Ltd.; LT95 refers to the time it takes for the device brightness to decay to 95%; all data are at 10mA / cm 2 Next test.

[0143] It can be seen from the device data results in Table 4 that, compared with device comparison examples 1-3, the current efficiency and device life in the devices of Examples 1-9 are higher than those of the comparison examples; compared with device comparison examples 4-6, the current efficiency and device life of the devices of Examples 10-18 are greatly improved relative to OLED devices of known materials.

[0144] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A nitrogen-doped fused ring resonance type organic compound, characterized in that: The structure of the nitrogen-doped fused ring resonance type organic compound is shown in the general formula (1): In the general formula (1), Z represents C-R1; Z1 represents C or N; Each occurrence of R1 is the same or different and represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, pyridyl, phenyl-substituted pyridyl, quinolyl, furyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl , tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy; M1 and M2 are independently substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 One of the heteroaryl groups; The substituent for the substituent group may be selected from one or more of a deuterium atom, a cyano group, a methyl group, a tert-butyl group, a phenyl group, and a biphenyl group.

2. The nitrogen-doped fused ring resonance type organic compound according to claim 1, characterized in that: The structure of the organic compound is shown in any one of the general formulas (2) to (11): In general formula (2) to general formula (11), Z has the same meaning as defined in claim 1; X represents O, S, Se, N(R2) or C(R3)(R4); R2 represents one of phenyl and biphenyl; R3 and R4 are independently represented by one of methyl, phenyl and biphenyl; Y is independently represented by CH or C(R5); R5 is selected from one or more of a deuterium atom, a cyano group, a methyl group, a tert-butyl group, a phenyl group, and a biphenyl group.

3. The nitrogen-doped fused ring resonance type organic compound according to claim 1, characterized in that: The structure of the organic compound is shown in any one of the general formulas (12) to (18): In general formula (12) to general formula (18), Z has the same meaning as defined in claim 1; X represents O, S, Se, N(R2) or C(R3)(R4); R2 represents one of phenyl and biphenyl; R3 and R4 are independently represented by one of methyl, phenyl and biphenyl; Y is independently represented by CH or C(R5); R5 is selected from one or more of a deuterium atom, a cyano group, a methyl group, a tert-butyl group, a phenyl group, and a biphenyl group.

4. The nitrogen-doped fused ring resonance type organic compound according to claim 1, characterized in that: The structure of the organic compound is shown in any one of the general formulas (19) to (26): In general formula (19) to general formula (26), Z represents C-R1; Each occurrence of R1 is the same or different and represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, pyridyl, phenyl-substituted pyridyl, quinolyl, furyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl , tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy; R a , R b , R c , R d Each occurrence of the same or different radicals may be represented by hydrogen atoms, deuterium atoms, substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, pyridyl, phenyl-substituted pyridyl, quinolyl, furyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl , tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy; Rd'、R e , R f Each occurrence of the same or different group is represented by one of a hydrogen atom, a deuterium atom, a cyano group, a methyl group, a tert-butyl group, a phenyl group, and a biphenyl group; X represents O, S, Se, N(R2) or C(R3)(R4); R2 represents one of phenyl and biphenyl; R3 and R4 are independently represented by one of methyl, phenyl and biphenyl; The substituents for the substituent group are selected from one or more of a deuterium atom, a cyano group, a methyl group, a tert-butyl group, a phenyl group, and a biphenyl group; Y is independently represented by CH or C(R5); R5 is selected from one or more of a deuterium atom, a cyano group, a methyl group, a tert-butyl group, a phenyl group, and a biphenyl group.

5. The nitrogen-doped fused ring resonance type organic compound according to claim 1, characterized in that: The R1 each time appears the same or different represents a hydrogen atom, a deuterium atom, an adamantyl group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a methyl substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a deuterated terphenyl group, a naphthyl group, a pyridyl group, a phenyl substituted pyridyl group, a quinolyl group, a furanyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a methyl substituted phenyl group, an ethyl substituted phenyl group, an isopropyl substituted Phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy.

6. The nitrogen-doped fused ring resonance type organic compound according to claim 2 or 3, characterized in that: The R1 each time appears the same or different represents a hydrogen atom, a deuterium atom, an adamantyl group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a methyl substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a deuterated terphenyl group, a naphthyl group, a pyridyl group, a phenyl substituted pyridyl group, a quinolyl group, a furanyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a methyl substituted phenyl group, an ethyl substituted phenyl group, an isopropyl substituted Phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy; The R2 is one of phenyl and biphenyl; The R3-R4 are independently represented by one of methyl, phenyl and biphenyl; The substituent for the substituent group may be selected from deuterium, methyl, tert-butyl, phenyl, biphenyl.

7. The nitrogen-doped fused ring resonance type organic compound according to claim 4, characterized in that: The R1 each time appears the same or different represents a hydrogen atom, a deuterium atom, an adamantyl group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a methyl substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a deuterated terphenyl group, a naphthyl group, a pyridyl group, a phenyl substituted pyridyl group, a quinolyl group, a furanyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a methyl substituted phenyl group, an ethyl substituted phenyl group, an isopropyl substituted Phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy; The R a , R b , R c , R d Each independently represents a hydrogen atom, a deuterium atom, an adamantyl group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a methyl-substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a deuterated terphenyl group, a naphthyl group, a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, a furanyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a methyl-substituted phenyl group, an ethyl-substituted phenyl group, an isopropyl-substituted phenyl group, a tert-butyl group One of butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, and tert-butoxy; Rd'、R e , R f Each occurrence of the same or different group is represented by one of a hydrogen atom, a deuterium atom, a cyano group, a methyl group, a tert-butyl group, a phenyl group, and a biphenyl group; The R2 is one of phenyl and biphenyl; The R3-R4 are independently represented by one of methyl, phenyl and biphenyl; The substituent for the substituent group may be selected from deuterium, methyl, tert-butyl, phenyl, biphenyl.

8. A nitrogen-doped fused ring resonance type organic compound, characterized in that: The specific structure of the organic compound is any one of the following structures:

9. An organic electroluminescent device, comprising a cathode and an anode, and an organic light-emitting functional layer therebetween, wherein the organic light-emitting functional layer comprises a light-emitting layer, characterized in that: The light-emitting layer contains the nitrogen-doped fused ring resonance type organic compound according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that: The light-emitting layer comprises a host material and a doping material, and the doping material comprises the nitrogen-doped fused ring resonance type organic compound according to any one of claims 1 to 8.

11. The organic electroluminescent device according to claim 9, wherein the light-emitting layer comprises a first host material, a second host material and a doping material, wherein: At least one of the first main material and the second main material is a TADF material, and the doping material is the nitrogen-doped condensed ring resonance type organic compound according to any one of claims 1 to 8.

12. The organic light-emitting device according to claim 9, wherein the light-emitting layer comprises a host material, an exciton sensitizing material and a doping material, wherein: The exciton sensitizing material is a complex containing a metal element, and the doping material is the nitrogen-doped condensed ring resonance type organic compound according to any one of claims 1 to 8.

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