WO2022242521A1 - Condensed azacyclic compound, use thereof, and organic electroluminescent device comprising condensed azacyclic compound - Google Patents

Abstract

Disclosed in the present invention are a condensed azacyclic compound, the use thereof, and an organic electroluminescent device comprising the condensed azacyclic compound. The condensed azacyclic compound has a structure of a combination of formulas (1) and (2), wherein Z1 to Z14 each are independently represented as CR1 to CR14 or N; when each of Z1 to Z14 on rings A to D is independently represented as N, the sum of the number of Ns on rings A to D is less than or equal to 4 and the number of Ns on each of rings A to D is less than or equal to 1; and when formula (1) is substituted with a substituent group represented by formula (2), the substitution only occurs in positions Z1, Z2, Z5, Z6, Z8, Z9, Z12 or Z13. The compound provided in the present invention can be used as a luminescent material for an organic electroluminescent device. The material has the characteristics of a high luminous efficiency and a narrow emission spectrum, and the luminous color purity, luminous efficiency, and service life of the device are improved.

Description

A kind of condensed nitrogen heterocyclic compound and its application and organic electroluminescent device comprising the compound technical field

The invention relates to the technical field of organic electroluminescence, in particular to a novel organic compound and its application, and an organic electroluminescent device containing the compound.

Background technique

Organic Light Emitting Devices (OLED: Organic Light Emitting Devices) is a current-driven thin-film device similar to a sandwich structure, with a single or multiple organic functional material layers sandwiched between the anode and cathode. Under the action of an electric field in an OLED, the holes generated by the anode and the electrons generated by the cathode will move, inject into the hole transport layer and the electron transport layer respectively, and migrate to the light-emitting layer. When the two meet and recombine in the light-emitting layer, a Energy excitons, which excite light-emitting molecules and eventually produce visible light. OLED has the characteristics of self-illumination, wide viewing angle, wide color gamut, short response time, high luminous efficiency, low operating voltage, low cost, and simple production process. It can be made into large-size and/or flexible ultra-thin panels, which is a development The new display technology with high speed and high process integration has been widely used in display products such as TVs, smart phones, tablet computers, vehicle displays, lighting, etc., and will be further applied in creative display products such as large-size displays and flexible screens .

Organic optoelectronic materials applied to OLED devices can be divided into light-emitting layer materials and auxiliary functional layer materials in terms of use. Among them, the light-emitting material layer materials include guest materials (also called light-emitting materials, doping materials) and host materials (also called According to different luminescent mechanisms, luminescent materials are divided into fluorescent materials, phosphorescent materials and thermally activated delayed fluorescent materials, and auxiliary functional layer materials are divided into electron injection materials and electron transport materials according to the different properties of electron or hole transport speeds. , Hole blocking materials, electron blocking materials, hole transport materials, hole injection materials.

Among the organic electroluminescent elements of various colors, the most studied and most important is the improvement of the performance of the light-emitting devices of the three primary colors of red, green, and blue. The light-emitting dopant used in the light-emitting layer has a decisive impact on the color, efficiency, stability and other properties of the electroluminescent device. However, light-emitting dopant materials with high efficiency and narrow emission are still in short supply. The current blue light-emitting doped materials have problems such as low efficiency, short lifespan and insufficient color purity, such as patent (CN200310124405.8, application date December 24, 2003) and literature (ACS Appl.Mater.Interfaces 2018, 10,30022-30028) in the pyrene compound, the pyrene molecule has a planar rigid π-conjugated structure, which is easy to achieve high luminous efficiency, and is a blue light-emitting dopant structure with excellent performance. However, on the one hand, its molecular structure is prone to intermolecular aggregation, resulting in reduced efficiency and lifetime; on the other hand, its emission spectrum presents a strong shoulder emission, resulting in a wide half-width of the spectrum and low color purity.

Therefore, there is an urgent need in this field to develop a class of OLED functional materials with high luminous efficiency and narrow emission spectrum. When this type of material is applied in organic electroluminescent devices, it has low driving voltage, high efficiency, long life, high color purity, etc. advantage.

Contents of the invention

In order to solve the above-mentioned technical problems, the present invention provides a novel fused nitrogen heterocyclic organic compound, which is composed of formula (1) and formula (2):

in,

In formula (1), Z ₁ to Z ₁₄ are independently represented as CR ₁ to CR ₁₄ or N; in formula (2), when the L bond is connected to Z ₁ to Z ₁₄ , then Z ₁ to Z ₁₄ are represented as C ;

When Z ₁ to Z ₁₄ on ring A to ring D are each independently expressed as N, the sum of the numbers of N on ring A to ring D is ≤4; and the number of N on ring A to ring D alone is ≤1;

Preferably, the structure of formula (1) is represented as follows:

The number of substituent groups represented by formula (2) when substituted by formula (1) is ≤4; and the number of substitutions of formula (2) on individual rings A to D is ≤1;

Preferably, when the substituent group represented by formula (2) is substituted by formula (1), it is only substituted at Z ₁ , Z ₂ , Z ₅ , Z ₆ , Z ₈ , Z ₉ , Z ₁₂ or Z ₁₃ ;

In formula (2), L is independently selected from single bonds, substituted or unsubstituted linear or branched alkylene groups with 1 to 20 carbon atoms, substituted or unsubstituted ring-forming carbon atoms with 3 to 20 Cycloalkylene, substituted or unsubstituted arylene with 6 to 30 ring carbon atoms, substituted or unsubstituted heteroarylene with 2 to 30 ring carbon atoms, substituted or unsubstituted Subfused aryl rings with 10 to 50 ring carbon atoms, substituted or unsubstituted subfused heterocyclic rings with 6 to 50 ring atoms;

Preferably, L is independently selected from the substituted or unsubstituted following groups, but not limited to the following groups:

Phenylene, naphthylene, fluorenylene, indenylene, indolylene, benzofurylene, benzothienylene;

In formula (1), R ₁ to R ₁₄ substituent groups are independently selected from hydrogen atom, deuterium atom, halogen atom, cyano group, nitro group, substituted silicon group, substituted or unsubstituted carbon atoms with 1 to 50 Alkyl, substituted or unsubstituted alkenyl with 1 to 20 carbons, substituted or unsubstituted alkynyl with 1 to 20 carbons, substituted or unsubstituted alkoxy with 1 to 50 carbons, substituted or unsubstituted Substituted fluoroalkyl with 1 to 20 carbons, substituted or unsubstituted fluoroalkoxy with 1 to 20 carbons, substituted or unsubstituted cycloalkyl with 3 to 50 ring carbon atoms, substituted or An unsubstituted aryl group with 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group with 5 to 50 ring atoms;

In formula (2), the substituent groups R ₁₅ to R ₁₆ are independently selected from substituted or unsubstituted alkyl groups with 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 50 ring carbon atoms , a substituted or unsubstituted aryl group with 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group with 5 to 50 ring atoms;

The substituent groups R ₁ to R ₁₆ can bond with each other to form a substituted or unsubstituted saturated or unsaturated ring, and can also form a substituted or unsubstituted saturated or unsaturated ring with an adjacent aromatic ring or heteroaryl ring. the fused ring;

Preferably, R ₁ to R ₁₆ substituent groups are independently selected from any one or more of the following groups:

Substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2-methylbutyl, substituted or unsubstituted n-pentyl, substituted or unsubstituted sec-pentyl, Substituted or unsubstituted trifluoromethyl, substituted or unsubstituted pentafluoroethyl, substituted or unsubstituted 2,2,2-trifluoroethyl, substituted or unsubstituted vinyl, substituted or unsubstituted propene substituted or unsubstituted n-butenyl, substituted or unsubstituted isobutenyl, substituted or unsubstituted n-pentenyl, substituted or unsubstituted isopentenyl, substituted or unsubstituted neopentenyl, Substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted n-butynyl, substituted or unsubstituted isobutynyl, substituted or unsubstituted n-pentynyl, substituted or unsubstituted Substituted isopentyl, substituted or unsubstituted neopentynyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclo Hexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracene substituted or unsubstituted phenanthrenyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted indenofluorenyl, substituted or unsubstituted Fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted or unsubstituted

substituted or unsubstituted naphthacene, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted diphenyl Thiolyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzoselenyl, substituted or unsubstituted carbazolyl, substituted or Unsubstituted indolo[3,2,1-jk]carbazolyl;

The "substituted" in "substituted or unsubstituted" in the above compounds means that the substituents are independently selected from deuterium atoms, tritium atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, monovalent alkyl groups with 1 to 10 carbon atoms Or a cycloalkyl group, a monovalent monocyclic aryl group or a fused ring aryl group with 6 to 30 carbon atoms, a monovalent heterocyclic group or a condensed ring heteroaryl group with a carbon number of 2 to 50;

Preferably, the "substituted" group in "substituted or unsubstituted" is independently any one or more selected from the following groups:

Deuterium atom, tritium atom, halogen atom, cyano group, nitro group, hydroxyl group, methyl group, methoxy group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group , 2-methylbutyl, cyclohexyl, adamantyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, deuterated phenyl, Fluorophenyl, methylphenyl, n-propylphenyl, tert-butylphenyl, trimethylphenyl, triphenylphenyl, tetraphenylphenyl, cyanophenyl, pyridyl, naphthyl , anthracenyl, biphenyl, biphenyl, terphenyl, fluorenyl, spirobifluorenyl, furyl, benzofuryl, dibenzofuryl, azadibenzofuryl, thienyl, Benzothienyl, dibenzothienyl, azadibenzothienyl, carbazolyl, phenylcarbazolyl, azacarbazolyl;

Further, the formula (1) and formula (2) protected by the present invention can preferably select the following specific structural compounds Compound 1～Chem 216, and these compounds are only representative:

The second object of the present invention is to provide an organic electroluminescent device. The organic electroluminescent device comprises an anode, a cathode and at least one layer of organic thin film between the anode and the cathode, and the organic thin film contains one or more organic electroluminescence compounds composed of formula (1) and formula (2). Luminescent compound. The organic layer includes a light-emitting layer and a functional layer, and the compound formed by the combination of formula (1) and formula (2) can be used alone or in combination as a hole injection layer, a hole transport layer or a light-emitting material.

The third object of the present invention is to provide an organic electroluminescent device. When the compound formed by the combination of formula (1) and formula (2) is applied in a device, an organic electroluminescent device with high color purity and low driving voltage, high efficiency and long life is obtained by optimizing the structure of the device.

Beneficial effects of the present invention:

The fused nitrogen heterocyclic compound protected by the present invention is a kind of amino-substituted bis-indolophenazine compound. This kind of material has a planar conjugated rigid structure, can inhibit the twisting of the structural unit in the excited state, and has a narrow emission spectrum, and has high luminous efficiency; the combination of the arylamine unit of formula (2) and the structure of formula (1) can adjust the energy level and band gap of the molecule to obtain fluorescence of a suitable wavelength, and at the same time, the steric hindrance of the arylamine unit, It is beneficial to inhibit the aggregation between material molecules and significantly improve the device performance.

Description of drawings

The drawings described here are used to provide a further understanding of the application and constitute a part of the application. The schematic embodiments and descriptions of the application are used to explain the application and do not constitute an improper limitation to the application. In the attached picture:

Fig. 1 is a schematic diagram of the structure of an organic electroluminescent device applied by the compound of the present invention, wherein, the meanings of each layer structure of the device are as follows:

1. Transparent substrate layer, 2. ITO anode layer, 3. Hole injection layer, 4. Hole transport layer A, 5. Hole transport layer B (or electron blocking layer), 6. Light emitting layer, 7. Electron transport Layer B (or hole blocking layer), 8, electron transport layer A, 9, electron injection layer, 10, cathode reflective electrode layer.

Figure 2 is the fluorescence spectrum of Comparative Compound-1 in toluene solution at room temperature [25°C, 300K].

Figure 3 is the fluorescence spectrum of Comparative Compound-2 in toluene solution at room temperature [25°C, 300K].

Figure 4 shows the fluorescence spectrum of CH66 in toluene solution at room temperature [25°C, 300K].

Detailed ways

The principles and features of the present invention will be further described below by taking a number of synthetic examples as examples. The given examples are only used to explain the present invention, but not to limit the scope of the present invention.

The synthesis methods of specific compounds of formula (1) listed below, unless otherwise stated, are all carried out in anhydrous solvents under a protective gas atmosphere.

Synthesis of Intermediate 1

Weigh 5.0g (20mmol) of 2-iodonitrobenzene, 4.83g (21mmol) of 5-bromo-2-methoxyphenylboronic acid, 0.66g (0.6mmol) of tetrakistriphenylphosphine palladium, 5.52g (40mmol) of potassium carbonate in a flask, add 40ml of toluene, 10ml of ethanol and 15ml of water, nitrogen bubbling deoxygenation for 10 minutes. Heated to 90°C and stirred at reflux for 12h. The reaction was stopped, cooled to room temperature, extracted three times with ethyl acetate/water, dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated on a silica gel column to obtain 5.48 g of the target product with a yield of 89%. The m/z=308.2 was determined by mass spectrometry.

Synthesis of Intermediate 2

Weigh 5.48g (17.8mmol) of intermediate 1 and 10.27g (39.2mmol) of triphenylphosphine into the flask, and then add 20ml of dichlorobenzene. Exhaust gas, nitrogen protection, 180 ° C under reflux reaction for 14h. The reaction was stopped, and dichlorobenzene was distilled off under reduced pressure. Separation on a silica gel column yielded 4.18 g of the target product with a yield of 85%. The molecular weight m/z=276.2 was measured by mass spectrometry.

Synthesis of intermediate 3

Weigh 2.76g (10.0mmol) of intermediate 2, 0.11g (0.5mmol) of palladium acetate, 0.23g (0.5mmol) of 2-dicyclohexylphosphine-2',6'-diisopropoxy-1 , 1'-biphenyl and 1.92g (20mmol) of sodium tert-butoxide in a flask, then add 30ml of toluene. Exhaust gas, nitrogen protection, reflux reaction at 120°C for 48h. Stop the reaction, cool to room temperature, extract with dichloromethane/water, and remove toluene by rotary evaporation. Recrystallized several times with ethyl acetate, and filtered to obtain 0.51 g of the target product with a yield of 26%. The molecular weight m/z=390.5 was determined by mass spectrometry.

Synthesis of Intermediate 4

Weighed 0.78g (2.0mmol) of Intermediate 3 and dissolved it in 40ml of anhydrous dichloromethane under nitrogen protection. The temperature dropped to -60°C, 0.77ml (8.0mmol) of boron tribromide was added dropwise, and the reaction was allowed to return to room temperature overnight. The reaction solution was slowly poured into ice water, and neutralized by adding sodium bicarbonate. The dichloromethane was removed by rotary evaporation, the crude product was obtained by filtration, and washed three times with ethanol. After drying, 0.54 g of the target product was obtained with a yield of 75%. The molecular weight m/z=362.2 was determined by mass spectrometry.

Synthesis of Intermediate 5

Weigh 0.72g (2.0mmol) of intermediate 4 and dissolve it in 40ml of anhydrous dichloromethane, add 0.8g (8.0mmol) of triethylamine and 1.13g (4mmol) of trifluoromethanesulfonic anhydride. Under nitrogen protection, stir overnight at room temperature. The reaction solution was poured into water, neutralized with sodium carbonate, and extracted with dichloromethane. Rotary evaporation, ethyl acetate recrystallization. 1.01 g of the target product was obtained by filtration with a yield of 81%. The molecular weight m/z=626.1 was determined by mass spectrometry.

Synthesis Example 1: Synthesis of Compound 2

Weigh 0.63g (1.0mmol) of intermediate 5, 0.51g (3.0mmol) of diphenylamine, 0.046g (0.05mmol) of tris(dibenzylideneacetone) dipalladium, 0.046g (0.20mmol) of tri-tertiary Butyl tetrafluoroborate and 0.29 g (3.0 mmol) of sodium tert-butoxide were added to 10 ml of toluene. Gas exchange, nitrogen protection, reflux reaction at 120°C overnight. Cool to room temperature, extract with dichloromethane/water, dry over anhydrous sodium sulfate, and concentrate by rotary evaporation. Separation on a silica gel column yielded 0.52 g of the target product P2, with a yield of 79%, and the molecular weight m/z=664.3 as measured by mass spectrometry.

Synthesis Example 2: Synthesis of Compound 39

The diphenylamine in the synthesis of compound 2 is replaced by N-(4-tert-butylphenyl)-dibenzofuran-4-amine, and the target product compound 39 can be obtained under the same reaction conditions, with a yield of 72%, as measured by mass spectrometry Molecular weight m/z = 956.5.

Synthesis of Intermediate 6

Weigh 11.4g (50mmol) of 2-bromo-4-tert-butylaniline and dissolve it in 50ml of acetic acid, add 5ml of concentrated hydrochloric acid, and stir at room temperature for 10 minutes. Lowered to 0°C, slowly added 3.8g (55mmol) of sodium nitrite, and stirred at low temperature for 0.5h. Then 22.5 g (100 mmol) of SnCl ₂ .2H ₂ O dissolved in concentrated hydrochloric acid was added dropwise into the reaction system. After the dropwise addition, slowly return to room temperature and stir for 2 h. The reaction was stopped, filtered, washed with water, and dried to obtain 11.3 g of crude product, which was directly used for the next reaction.

Synthesis of Intermediate 7

Weigh 11.3g (40.5mmol) of intermediate 6, 4.76g (48.6mmol) of cyclohexanone and 13.78g (80mmol) of p-toluenesulfonic acid, dissolve them in 80ml of ethanol, and react at reflux at 80°C for 6h. Stop the reaction, cool to room temperature, and remove ethanol by rotary evaporation. Dissolve in ethyl acetate, neutralize with sodium carbonate solution, and extract with ethyl acetate. Dry over anhydrous sodium sulfate and concentrate by rotary evaporation. Silica gel column separation obtained 10.2 g of the target product with a yield of 82%. The molecular weight m/z=305.1 was measured by mass spectrometry.

Synthesis of Intermediate 8

9.18g (30mmol) of intermediate 7 and 1.53g (9mmol) of copper chloride dihydrate were weighed and dissolved in 40ml of DMSO. Under nitrogen protection, react at 120°C for 12h. Cool to room temperature, add 100ml of ethyl acetate, wash with water 4 times, dry over anhydrous sodium sulfate, and remove the solvent by rotary evaporation. Separation on a silica gel column yielded 7.7 g of the target product with a yield of 85%, and the molecular weight m/z = 301.1 as measured by mass spectrometry.

Synthesis of Intermediate 9

Weigh 3.0 g (10 mmol) of intermediate 8, 0.38 g (2 mmol) of CuI, 0.12 g (2 mmol) of copper powder and 4.17 g (30 mmol) of potassium carbonate in a flask, and add 30 ml of dichlorobenzene. Exhaust gas, nitrogen protection, reflux reaction at 180°C for 48h. The reaction was stopped, and dichlorobenzene was distilled off under reduced pressure. Dichloromethane was dissolved, washed three times with water, dried over anhydrous sodium sulfate, and dried by rotary evaporation. Separation on a silica gel column yielded 0.98 g of the target product with a yield of 45%. The molecular weight m/z=442.3 was measured by mass spectrometry.

Synthesis of intermediate 10

Weigh 0.88g (2.0mmol) of Intermediate 9 and dissolve it in 60ml of chloroform, and stir at room temperature in the dark. Add 0.71 g (4.0 mmol) of NBS in batches and react overnight at room temperature. Stop the reaction, pour the reaction solution into aqueous sodium bicarbonate solution, and wash with water three times. It was dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and recrystallized three times from chloroform/ethanol to obtain 0.46 g of the target product with a yield of 38%. The molecular weight m/z=598.1 was determined by mass spectrometry.

Synthesis Example 3: Synthesis of Compound 66

Weigh 0.60g (1.0mmol) of intermediate 10, 0.63g (3.0mmol) of N-(4-isopropylphenyl)aniline, 0.046g (0.05mmol) of tris(dibenzylideneacetone)dipalladium , 0.046g (0.20mmol) of tri-tert-butyltetrafluoroborate and 0.29g (3.0mmol) of sodium tert-butoxide were added to 10ml of toluene. Gas exchange, nitrogen protection, reflux reaction at 120°C overnight. Cool to room temperature, extract with dichloromethane/water, dry over anhydrous sodium sulfate, and concentrate by rotary evaporation. Silica gel column separation to obtain the target product 66 0.62g, the yield was 72%, and the molecular weight m/z=860.5 was measured by mass spectrometry.

Synthesis of Intermediate 11

Weigh 6.75g (50mmol) of 4-isopropylaniline, 14.2g (50mmol) of 1-bromo-4-phenylnaphthalene, 0.09g (0.1mmol) of three (dibenzylidene acetone) dipalladium, 0.09 g (0.4 mmol) of tri-tert-butyltetrafluoroborate and 6.72 g (70 mmol) of sodium tert-butoxide were added to 80 ml of toluene. Exhaust gas, nitrogen protection, 80 ℃ reaction 4h. Cool to room temperature, extract with dichloromethane/water, dry over anhydrous sodium sulfate, and concentrate by rotary evaporation. Silica gel column separation obtained 13.7 g of the target product with a yield of 81%. The molecular weight m/z=337.2 was measured by mass spectrometry.

Synthesis Example 4: Synthesis of Compound 94

N-(4-isopropylphenyl)aniline in the synthesis of compound 66 was replaced by intermediate 11, and the target compound compound 94 could be obtained under the same reaction conditions with a yield of 65%, and the molecular weight m/z=1112.7 as measured by mass spectrometry.

Synthesis of intermediate 12

Weigh 4.46g (20mmol) 2-bromophenylhydrazine hydrochloride, 4.2g (24mmol) 4-phenylcyclohexanone dissolved in 40ml ethanol, add 4.2g (24mmol) 4-toluenesulfonic acid, reflux reaction at 80°C 6h. Stop the reaction, cool to room temperature, remove ethanol by rotary evaporation, extract three times with ethyl acetate/water, dry over anhydrous sodium sulfate, spin to dry the solvent, and separate on a silica gel column to obtain 4.43g of the target product with a yield of 68%. The molecular weight was measured by mass spectrometry m/ z = 325.1.

Synthesis of Intermediate 13

Weigh 4.9g (15mmol) of intermediate 12 and dissolve it in 30ml of toluene, add 13.6g (60mmol) of DDQ, heat to 120°C, reflux and stir for 12h. Cool to room temperature, add sodium carbonate aqueous solution, extract with ethyl acetate, collect the organic phase, dry over anhydrous sodium sulfate, spin to dry the solvent, and separate on a silica gel column to obtain 3.38 g of the target product with a yield of 70%. The molecular weight m/z = 321.1.

Synthesis of Intermediate 14

Weigh 3.2g (10mmol) of intermediate 13, 0.38g (2mmol) of CuI, 0.12g (2mmol) of copper powder and 4.17g (30mmol) of potassium carbonate in a flask, and add 30ml of dichlorobenzene. Exhaust gas, nitrogen protection, reflux reaction at 180°C for 48h. The reaction was stopped, and dichlorobenzene was distilled off under reduced pressure. Dichloromethane was dissolved, washed three times with water, dried over anhydrous sodium sulfate, and dried by rotary evaporation. Separation on a silica gel column yielded 0.77 g of the target product with a yield of 32%. The molecular weight m/z=482.2 was measured by mass spectrometry.

Synthesis of Intermediate 15

Weigh 0.96g (2.0mmol) of intermediate 14 and dissolve it in 100ml THF, and stir at room temperature in the dark. Add 0.71 g (4.0 mmol) of NBS in batches and react overnight at room temperature. Stop the reaction, pour the reaction solution into aqueous sodium bicarbonate solution, and wash with water three times. It was dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and recrystallized three times from chloroform/ethanol to obtain 0.60 g of the target product with a yield of 47%. The molecular weight m/z=638.1 was determined by mass spectrometry.

Synthesis Example 5: Synthesis of Compound 34

Weigh 0.64g (1.0mmol) of intermediate 15, 0.76g (3.0mmol) of N-(4-tert-butylphenyl)-2,4-dimethylaniline, 0.046g (0.05mmol) of tris( Dibenzylideneacetone) dipalladium, 0.046 g (0.20 mmol) of tri-tert-butyltetrafluoroborate and 0.29 g (3.0 mmol) of sodium tert-butoxide were added to 10 ml of toluene. Gas exchange, nitrogen protection, reflux reaction at 120°C overnight. Cool to room temperature, extract with dichloromethane/water, dry over anhydrous sodium sulfate, and concentrate by rotary evaporation. Silica gel column separation to obtain the target product 34 0.67g, the yield was 68%, and the molecular weight m/z=984.5 was measured by mass spectrometry.

Synthesis of Intermediate 21

Weigh 7.47g (30mmol) of 2-iodonitrobenzene, 5.7g (33mmol) 2-boronic acid-4-fluoro-1-chlorobenzene, 0.1g (1.0mmol) tetrakistriphenylphosphine palladium, 8.3g (60mmol) ) Potassium carbonate was dissolved in toluene/ethanol/water (60/20/20ml), and nitrogen gas was bubbled for 10 minutes. Heated to 90 ° C reflux reaction for 12h. Cool to room temperature, extract with ethyl acetate, collect the organic phase, dry over anhydrous sodium sulfate, and dry by rotary evaporation. Separation on a silica gel column yielded 5.85 g of the target product with a yield of 78%. The molecular weight m/z=250.7 was measured by mass spectrometry.

Synthesis of Intermediate 22

Weigh 5.0g (20mmol) of intermediate 21, 7.96g (20mmol) of 1-bromo-3,6-diphenylcarbazole, (40mmol) 13.0g of cesium carbonate dissolved in 50ml of DMAc, pump gas, nitrogen protection , 160°C for 24h. Cool to room temperature, pour into water, extract with dichloromethane, and spin dry the solvent. Silica gel column separation obtained 7.16 g of the target product, with a yield of 57%, and the molecular weight m/z=628.1 as measured by mass spectrometry.

Synthesis of Intermediate 23

Weigh 6.3g (10mmol) of intermediate 22 and 7.9g (30mmol) of triphenylphosphine dissolved in 30ml of dichlorobenzene, nitrogen protection, reflux at 180°C for 24h. After cooling to room temperature, dichlorobenzene was distilled off under reduced pressure. Ethyl acetate and water were extracted three times, the organic phase was collected, and the solvent was spin-dried. Silica gel column separation obtained 4.11 g of the target product with a yield of 69%. The molecular weight m/z=596.1 was measured by mass spectrometry.

Synthesis of Intermediate 24

Weigh 6.0g (10mmol) of intermediate 23, 0.38g (2mmol) of cuprous iodide, 4.9g (15mmol) of cesium carbonate and dissolve in 30ml of dichlorobenzene, nitrogen protection, reflux at 180°C for 24h. After cooling to room temperature, dichlorobenzene was distilled off under reduced pressure. Ethyl acetate and water were extracted three times, the organic phase was collected, and the solvent was spin-dried. Silica gel column separation obtained 2.17 g of the target product, with a yield of 42%, and the molecular weight m/z = 516.2 as measured by mass spectrometry.

Synthesis Example 6: Synthesis of Compound 147

Weigh 0.52g (1.0mmol) of intermediate 20, 0.76g (3.0mmol) of N-phenyl-3 (9,9-dimethyl-9H-fluorene) amine, 0.046g (0.05mmol) of tris( Dibenzylideneacetone) dipalladium, 0.046 g (0.20 mmol) of tri-tert-butyltetrafluoroborate and 0.29 g (3.0 mmol) of sodium tert-butoxide were added to 10 ml of toluene. Gas exchange, nitrogen protection, reflux reaction at 120°C overnight. Cool to room temperature, extract with dichloromethane/water, dry over anhydrous sodium sulfate, and concentrate by rotary evaporation. Silica gel column separation to obtain the target product 147 0.57g, yield 75%, the molecular weight m/z=765.3 as measured by mass spectrometry.

Synthesis of Intermediate 25

Weigh 5.61g (20mmol) of 2,4-dibromo-3-nitropyridine, 3.28g (21mmol) 4-chlorophenylboronic acid, 0.1g (1.0 mmol) tetrakistriphenylphosphine palladium, 5.5g (40mmol) Potassium carbonate was dissolved in toluene/ethanol/water (50/20/20ml) and nitrogen was bubbled for 10 minutes. Heated to 90 ° C reflux reaction for 12h. Cool to room temperature, extract with ethyl acetate, collect the organic phase, dry over anhydrous sodium sulfate, and dry by rotary evaporation. Separation on a silica gel column yielded 4.49 g of the target product with a yield of 72%. The molecular weight m/z=311.9 was determined by mass spectrometry.

Synthesis of Intermediate 26

Weigh 3.12g (10mmol) of intermediate 25 and 7.9g (30mmol) of triphenylphosphine dissolved in 30ml of dichlorobenzene, under nitrogen protection, and react at reflux at 180°C for 24h. After cooling to room temperature, dichlorobenzene was distilled off under reduced pressure. Ethyl acetate and water were extracted three times, the organic phase was collected, and the solvent was spin-dried. Silica gel column separation obtained 1.71 g of the target product, with a yield of 61%, and the molecular weight m/z=279.9 as measured by mass spectrometry.

Synthesis of Intermediate 27

Weigh 2.8g (10mmol) of intermediate 23, 0.38g (2mmol) of cuprous iodide, and 4.14g (30mmol) of potassium carbonate dissolved in 30ml of dichlorobenzene, nitrogen protection, and reflux at 180°C for 48h. After cooling to room temperature, dichlorobenzene was distilled off under reduced pressure. Ethyl acetate and water were extracted three times, the organic phase was collected, and the solvent was spin-dried. Silica gel column separation obtained 1.14 g of the target product, with a yield of 57%, and the molecular weight m/z = 400.0 as measured by mass spectrometry.

Synthesis Example 7: Synthesis of Compound 170

Weigh 0.40g (1.0mmol) of intermediate 27, 0.76g (3.0mmol) of N-(4-tert-butylphenyl)-4-dibenzofuranamine, 0.046g (0.05mmol) of three (di Benzylideneacetone) dipalladium, 0.046 g (0.20 mmol) of tri-tert-butyltetrafluoroborate and 0.29 g (3.0 mmol) of sodium tert-butoxide were added to 15 ml of toluene. Gas exchange, nitrogen protection, reflux reaction at 120°C overnight. Cool to room temperature, extract with dichloromethane/water, dry over anhydrous sodium sulfate, and concentrate by rotary evaporation. Silica gel column separation obtained the target product 170 0.60g, the yield was 63%, and the molecular weight m/z=958.4 was measured by mass spectrometry.

Synthesis Example 8: Synthesis of Compound 180

The synthesis steps of intermediate 10 are the same, and the initial raw material 2-bromo-4-tert-butylaniline is replaced by 2-bromo-4,5-dimethylaniline, and intermediate 20 can be obtained, and the molecular weight m/z is measured by mass spectrometry = 542.1.

Weigh 0.54g (1.0mmol) of intermediate 20, 0.77g (3.0mmol) of N-(4-dibenzofuran)-aniline, 0.046g (0.05mmol) of tris(dibenzylideneacetone)dipalladium , 0.046g (0.20mmol) of tri-tert-butyltetrafluoroborate and 0.29g (3.0mmol) of sodium tert-butoxide were added to 10ml of toluene. Gas exchange, nitrogen protection, reflux reaction at 120°C overnight. Cool to room temperature, extract with dichloromethane/water, dry over anhydrous sodium sulfate, and concentrate by rotary evaporation. Separation on a silica gel column yielded the target product H180, about 0.55 g, with a yield of 61%, and the molecular weight m/z=900.4 as measured by mass spectrometry.

The functions of the film layers of the organic electroluminescence device involved are described below according to the preferred solution of the present invention.

The organic electroluminescence device described in the solution of the present invention comprises an anode layer, a cathode layer and at least one organic layer between the anode and the cathode. Alternatively, the organic layer is a film layer formed by laminating multiple layers of organic compounds. The organic layer may also contain inorganic compounds.

At least one of the organic layers of the organic electroluminescent device described in the solution of the present invention is a light-emitting layer. In addition to the light-emitting layer, the organic layer may also include other functional layers, for example, there may be one or more hole injection layers, hole transport layers, or electron blocking layers between the anode layer and the light-emitting layer, and between the two light-emitting layers It is also feasible to have an exciton blocking layer or an intermediate layer with similar functions, and one or more hole blocking layers, electron transport layers, or electron injection layers exist between the light emitting layer and the cathode layer. It should be noted that these functional layers do not necessarily exist.

The organic electroluminescent device of the present invention can be a fluorescent or phosphorescent device, or a fluorescent and phosphorescent hybrid device; it can be a single light-emitting device, or a series device with a plurality of light-emitting units; in addition, it can be It is a single-color light-emitting device, or a mixed-color device, or a white light-emitting device.

The light emitting layer may contain multiple guest materials and multiple host materials. The guest material may be a fluorescent material, a phosphorescent material and/or a thermally activated delayed fluorescent material. The host material refers to the host material that occupies most of the components in the light-emitting layer. The host material that is doped and combined with fluorescent materials is called "fluorescent host", and the host material that is doped and combined with phosphorescent materials is called "phosphorescent host". ". It should be noted that the selection of the host material does not depend on its molecular structure, but on the basis of the host material as the guest material.

The compounds of the invention according to the above embodiments can be used in different organic layers. Preference is given to organic electroluminescent devices in which the compounds according to the invention are used as hole-injection material, hole-transport material or emitting material of the emitting layer. The use of the compounds according to the invention according to the above embodiments is likewise suitable for use in organic electronic devices.

In a preferred embodiment of the invention, the compounds according to the invention are used as light-emitting materials for the light-emitting layer in organic electroluminescent devices.

The person skilled in the art generally knows these methods and can apply them without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

The application effects of the compounds of the present invention in organic electroluminescent devices are described in detail below through Device Examples 1-8 and Device Comparative Examples 1-2, so as to verify the technical progress and beneficial effects of the compounds of the present invention in this field. Embodiment and comparative example just set forth the present invention in further detail, but the description of the present invention is not limited by technical conditions.

Device Examples 1-8: Manufacture of an organic electroluminescent device used as a blue light-emitting material for the light-emitting layer

A 25mm×75mm×1.1mm thick glass substrate with an indium tin oxide (ITO) transparent electrode (anode) was ultrasonically cleaned in isopropanol for 5 minutes, followed by ultraviolet (UV)-ozone cleaning for 30 minutes. The film thickness of ITO was 130 nm. Install the above-mentioned glass substrate after cleaning on the substrate frame of the vacuum evaporation device, evacuate to 1×10 ^-5 ~ 1×10 ^-6 Pa, evaporate the hole injection layer (HIL) HATCN on the ITO transparent conductive layer, The film thickness is 15 nm. A hole transport layer A (HTL) was vapor-deposited on the hole injection layer to have a film thickness of 60 nm. Then, an electron blocking layer (EBL) was vapor-deposited on the hole transport layer A to have a film thickness of 5 nm. Then, a light-emitting layer (EML) was co-deposited on the electron blocking layer with a film thickness of 20 nm. The light-emitting layer (EML) adopts multi-source co-evaporation to evaporate the light-emitting material BD and the host material BH of the light-emitting layer, wherein the doping concentration of the light-emitting material is 2% by weight. In order to ensure the accuracy of the doping concentration of the luminescent material, it is necessary to wait for the evaporation rate of the luminescent material and the host material to stabilize before opening the shielding partition for multi-source co-evaporation. Then, a hole blocking layer (HBL) was vapor-deposited on the light-emitting layer to a film thickness of 5 nm. Then an electron transport material (ETL) and 8-hydroxyquinolate lithium (Liq) were evaporated on the hole blocking layer with a film thickness of 30 nm and a doping ratio of 1:1. Then, an electron-injecting electrode (EIL) Liq was vapor-deposited on the ETL to a film thickness of 1 nm. Then, a metal cathode aluminum (Al) was vapor-deposited on the EIL to a film thickness of 100 nm. The structure of the organic electroluminescent device in Example 1 is shown in Figure 1, and Figure 1 also shows the stacking sequence and function of each functional layer. The molecular structures of the materials used in OLEDs are shown in Table 1.

Table 1 Materials used in OLEDs

The device structure of the device embodiment 1 is specifically: ITO (130)/HATCN (15)/HTL (60)/EBL (5)/BH:2 (20, weight 2%)/HBL (5)/ETL: Liq(30, 50% by weight)/Liq(1)/Al(100), it should be noted that the numbers in parentheses represent the film thickness (unit: nm).

The difference between Device Example 2-Device Example 8 and Device Example 1 is that the Compound 2 of the present invention used in the light-emitting layer is replaced by other compounds of the present invention, see Table 2 for details.

Compared with Device Example 1, Comparative Examples 1-2 differ in that the luminescent material in the organic electroluminescent device is changed to Comparative Compound-1-Comparative Compound-2, and the device performance test data obtained are shown in Table 2.

The OLEDs were characterized by standard methods. For this purpose, the electroluminescence spectrum, current efficiency (measured in cd/A), power efficiency (measured in lm/W) and external quantum efficiency (EQE, measured in %) were determined as a function of luminous density from the Calculation of current/voltage/luminous density characteristic lines (IUL characteristic lines) of primary emission characteristics. Determine the required voltage V10 at a current density of 10 mA/ ^cm2 . Finally, EQE represents the external quantum efficiency at a current density of 10mA/ ^cm2 , T95 represents the working time of the device when the brightness of the device is reduced to 95% at a current density of 10mA/ ^cm2 , and the CIE coordinates are the device at 10mA/ ^cm2 CIE1931 chromaticity coordinates (x, y) calculated from electroluminescence spectrum at current density.

Table 2

It can be seen from Table 2 that the EQE efficiency and T95 of the device of Compound 1 are 6.8% and 82h, respectively, which is mainly due to the reduction in efficiency and aging of the device due to the aggregation of luminescent molecules (ACS Appl.Mater.Interfaces 2018,10,30022 -30028). For the device of comparative compound 2, the EQE efficiency and T95 lifetime of the device are lower, only 3.6% and 46h, respectively. After using the molecule of the present invention as the dopant of the light-emitting layer, the performance of its electroluminescent device is significantly improved, especially the efficiency and lifespan. For example, the EQE efficiency of the device embodiment 2 made by applying CH39 can reach 8.9%. Compared with device embodiment 1, it is improved by 30.8%, and compared with device embodiment 2, it is improved by 147%. However, the T95 life of the device embodiment 4 made by applying the chemical 94 can reach 129 hours, which is 57% higher than that of the device embodiment 1 and 180% higher than that of the device embodiment 2.

Physical data

Comparative compound 1, comparative compound 2 and CH66 were measured using a spectrofluorophotometer manufactured by Hitachi High-Tech Co., Ltd., a fluorescence spectrometry device, and the test samples were dissolved in a solvent (toluene) (1*10 ^-5 [mol/L of the concentration] ]), at room temperature (300 [K]), add 360nm excitation light to the sample added in the quartz colorimetric cell, test the fluorescence spectrum, you can get its luminescence peak and half-peak width, as shown in Table 3. Then, the luminescence quantum efficiency (PLQY) of the sample was measured using an absolute PL quantum yield measuring device manufactured by Hamamatsu Photonics.

table 3

sample	Luminous wavelength(nm)	Width at half maximum (nm)	PLQY(%)
Comp 1	463	41	87
Comp 2	428	37	56
Chemical 66	457	twenty one	91

The fluorescence spectrum of the toluene solution of comparative compound-1 is as shown in Figure 2, and its fluorescence peak is 463nm, and luminous efficiency (PLQY) can reach 87%; There are many long-wavelength components, which leads to the color coordinate CIEy of its electroluminescent device as high as 0.15, and the color purity of blue light is not high.

The fluorescence spectrum of the toluene solution of comparative compound-2 is shown in Figure 3, and the half-peak width of the fluorescence spectrum is 37nm, which is still relatively broad. However, its fluorescence peak is 428nm, so that the color coordinate CIEy of its electroluminescent device can be as low as 0.04, and the color purity of blue light is high. However, its luminous efficiency (PLQY) is only 56%, resulting in significantly low efficiency and lifetime of the electroluminescent device.

The fluorescence spectrum of the toluene solution of 66 of the present invention is shown in Figure 4, the fluorescence peak of its fluorescence spectrum is 457nm, half-maximum width is 21nm, very narrow blue light emission. Therefore, the color coordinate CIEy of its electroluminescent device is as low as 0.07, and the color purity of blue light is high. At the same time, its luminous efficiency (PLQY) is as high as 91%, so that the efficiency and service life of its electroluminescent device are obviously improved. It can be seen that the compound 66 of the present invention has a PLQY and emission wavelength similar to that of the comparative compound 1 of the prior art, but its half-peak width is significantly reduced. At the same time, compared with comparative compound 2, after the molecules of the present invention are connected with aniline units, in addition to the red shift of the luminescence wavelength, the half-peak width is significantly reduced and the luminous efficiency is significantly improved.

Claims (10)

1. A fused nitrogen heterocyclic compound, characterized in that the compound is composed of a combination of formula (1) and formula (2):

   

   in,

   In formula (1), Z ₁ to Z ₁₄ are independently represented as CR ₁ to CR ₁₄ or N; in formula (2), when the L bond is connected to Z ₁ to Z ₁₄ , then Z ₁ to Z ₁₄ are represented as C ;

   When Z ₁ to Z ₁₄ on ring A to ring D are each independently expressed as N, the sum of the numbers of N on ring A to ring D is ≤4; and the number of N on ring A to ring D alone is ≤1;

   The number of substituent groups represented by formula (2) when substituted by formula (1) is ≤4; and the number of substitutions of formula (2) on individual rings A to D is ≤1;

   L is independently selected from single bonds, substituted or unsubstituted linear or branched alkylene groups with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene groups with 3 to 20 ring carbon atoms, A substituted or unsubstituted arylene group with 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroarylene group with 2 to 30 ring carbon atoms, a substituted or unsubstituted ring carbon atom with 10 ~50 sub-fused aryl rings, substituted or unsubstituted sub-fused heterocyclic rings with 6-50 ring atoms;

   R ₁ to R ₁₄ substituent groups are independently selected from hydrogen atom, deuterium atom, halogen atom, cyano group, nitro group, substituted silicon group, substituted or unsubstituted alkyl group with 1 to 50 carbon atoms, substituted or unsubstituted Substituted alkenyl with 1 to 20 carbons, substituted or unsubstituted alkynyl with 1 to 20 carbons, substituted or unsubstituted alkoxy with 1 to 50 carbons, substituted or unsubstituted alkoxy with 1 to 20 carbons 20 fluoroalkyl groups, substituted or unsubstituted fluoroalkoxy groups with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 50 ring carbon atoms, substituted or unsubstituted ring carbon atoms An aryl group with 6 to 50 atoms, or a substituted or unsubstituted monovalent heterocyclic group with 5 to 50 ring atoms;

   R ₁₅ to R ₁₆ substituent groups are independently selected from substituted or unsubstituted alkyl groups with 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 50 ring carbon atoms, substituted or unsubstituted An aryl group with 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group with 5 to 50 ring atoms;

   The substituent groups R ₁ to R ₁₆ can bond with each other to form a substituted or unsubstituted saturated or unsaturated ring, and can also form a substituted or unsubstituted saturated or unsaturated ring with an adjacent aromatic ring or heteroaryl ring. of fused rings.
2. The condensed nitrogen heterocyclic compound according to claim 1, characterized in that, the preferred structure of formula (1) is as follows:

   

   Wherein, the definitions of R ₁ to R ₁₄ are as defined in claim 1 for formula (1).
3. The fused nitrogen heterocyclic compound according to claim 1, characterized in that, when the substituent group represented by formula (2) is substituted by formula (1), only Z ₁ , Z ₂ , Z ₅ , Z ₆ , Substitution at the Z ₈ , Z ₉ , Z ₁₂ or Z ₁₃ position.
4. The fused nitrogen heterocyclic compound according to claim 1, wherein L in the formula (2) is independently selected from a single bond, or any one or more of the following substituted or unsubstituted groups Species: phenylene, naphthylene, fluorenylene, indenylene, indolylene, benzofurylene, benzothienylene.
5. The fused nitrogen heterocyclic compound according to claim 1, wherein the R ₁ to R ₁₆ substituent groups are independently selected from any one or more of the following groups:

   Substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2-methylbutyl, substituted or unsubstituted n-pentyl, substituted or unsubstituted sec-pentyl, Substituted or unsubstituted trifluoromethyl, substituted or unsubstituted pentafluoroethyl, substituted or unsubstituted 2,2,2-trifluoroethyl, substituted or unsubstituted vinyl, substituted or unsubstituted propene substituted or unsubstituted n-butenyl, substituted or unsubstituted isobutenyl, substituted or unsubstituted n-pentenyl, substituted or unsubstituted isopentenyl, substituted or unsubstituted neopentenyl, Substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted n-butynyl, substituted or unsubstituted isobutynyl, substituted or unsubstituted n-pentynyl, substituted or unsubstituted Substituted isopentyl, substituted or unsubstituted neopentynyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclo Hexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracene substituted or unsubstituted phenanthrenyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted indenofluorenyl, substituted or unsubstituted Fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted or unsubstituted

   

   substituted or unsubstituted naphthacene, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted diphenyl Thiolyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted dibenzoselenyl, substituted or unsubstituted carbazolyl, substituted or Unsubstituted indolo[3,2,1-jk]carbazolyl;

   In addition, R ₁ ~ R ₁₄ substituent groups can also be selected from any one or more of the following groups: hydrogen atom, deuterium atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, substituted silicon base.
6. The condensed nitrogen heterocyclic compound according to claim 1, wherein the "substituted" in "substituted or unsubstituted" in the compound means that the substituents are independently selected from deuterium atoms, tritium atoms, halogen atoms, cyano group, nitro group, hydroxyl group, monovalent alkyl group or cycloalkyl group with 1 to 10 carbon atoms, monovalent monocyclic aryl group or condensed ring aryl group with 6 to 30 carbon atoms, aryl group with 2 to 50 carbon atoms Monovalent heterocyclic group or condensed ring heteroaryl group.
7. The fused nitrogen heterocyclic compound according to claim 1, wherein the condensed nitrogen heterocyclic compound is selected from the following structures:

   

   

   

   

   

   

   

   

   

   

   
8. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises an anode, a cathode and at least one layer of organic thin film between the anode and the cathode, and the organic thin film contains the organic thin film according to claims 1～ The compound described in any one of 7.
9. The organic electroluminescent device according to claim 8, wherein the organic thin film comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an exciton blocking layer, a hole blocking layer, an electron blocking layer, and an electron blocking layer. Any one or a combination of at least two of the transport layer, the electron injection layer, and at least one of the hole injection layer, the hole transport layer, and the light-emitting layer contains the compound described in any one of claims 1-8.
10. The organic electroluminescent device according to claim 8 or 9, characterized in that the compound is selected to be used as a hole injection material, a hole transport material or a fluorescent material of the light emitting layer in the organic electroluminescent device.

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