A novel triarylamine compound and application thereof, and an organic electroluminescent device comprising the same

Abstract

The application relates to a novel triarylamine compound with two carbazole units introduced on a biphenyl-triarylamine and application thereof, wherein, by fixing one of the carbazole units at the ortho position of the biphenyl in the triarylamine, a twisted structure is formed, thus effectively inhibiting the aggregation of the molecule, so that a stable dense film is formed; by changing the position of the other carbazole and the structure of the other two aryl groups of the triarylamine, the energy level barrier and the hole mobility can be effectively regulated, and the efficiency and the service life of the device are improved. Meanwhile, the double-carbazole system can more effectively inhibit the diffusion of electrons from the light-emitting layer to the hole side, so that the service life of the device is further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescence, in particular to a novel organic compound and application thereof, and an organic electroluminescent device comprising the compound. BACKGROUND

[0002] An OLED light-emitting device comprises a cathode and an anode and an organic layer therebetween, and the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. For the organic layer, appropriate mobility and energy level are key factors for realizing effective and rapid transport of electrons and holes, recombination of excitons and then light emission among different layer materials. At present, OLED display technology has been applied in the fields of smart phones, tablet computers, televisions and the like. However, compared with the actual product application requirements, low voltage, high efficiency and long service life of the OLED device are still the goals of product performance pursuit. In order to continuously improve the performance of the OLED device, it is necessary to continuously innovate the OLED device structure and manufacturing process, and it is more necessary to continuously research and innovate the OLED material itself, and to prepare a higher performance OLED material.

[0003] OLED optoelectronic materials can be divided into two categories in terms of use, namely charge transport layer materials and light-emitting layer materials. Further, the charge transport layer materials can be further divided into electron injection, transport layer materials, electron blocking layer materials, hole injection, transport layer materials and hole blocking layer materials, and the light-emitting layer materials can be further divided into host materials and doped light-emitting materials. In order to manufacture high-performance OLED light-emitting devices, various organic functional materials are required to have good optoelectronic properties, for example, as a charge transport layer material, it is required to have good carrier mobility, appropriate HOMO / LUMO energy level, high glass transition temperature and the like; as a light-emitting layer host material, the material is required to be stable to light and electricity, and to have appropriate HOMO / LUMO energy level and the like.

[0004] Common OLED device structures include hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer and other film layers, that is, the organic OLED material applied to the OLED device at least contains hole injection material, hole transport material, light emitting material, electron transport material and the like, therefore, the material type and collocation form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the OLED material used has strong selectivity, and the performance of the same material in different structure devices may be completely different. Therefore, in view of the current industrial application requirements of OLED devices, and the light and electrical characteristics requirements of different functional film layers of OLED devices, it is necessary to select a material or material combination that is more suitable and has high performance, so as to realize the comprehensive characteristics of low voltage, high efficiency and long service life of the device. In terms of the actual needs of the current OLED display and lighting industry, the development of OLED materials is still far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is particularly important to develop higher performance organic functional materials. SUMMARY

[0005] The present application aims to solve the above technical problems, and relates to a novel triarylamine compound with two carbazole units introduced on a biphenyl-triarylamine and applications thereof. One of the carbazole units is fixed at the ortho position of the biphenyl in the triarylamine to form a twisted structure, thereby effectively inhibiting the aggregation of the molecule, forming a stable and dense film. By changing the position of the other carbazole and the structure of the other two aryl groups of the triarylamine, the energy level barrier and the hole mobility can be effectively regulated, and the efficiency and service life of the device can be improved. At the same time, the double carbazole system can more effectively inhibit the diffusion of electrons from the light emitting layer to the hole side, thereby further improving the service life of the device.

[0006] Specifically, the present application provides: 1) a triarylamine compound for an organic electroluminescent device, wherein the compound is represented by formula (1):

[0007]

[0008] wherein one of R1 to R4 is a carbazolyl group, and the others are each independently hydrogen or deuterium, wherein all the hydrogen atoms on the carbazolyl group are hydrogen, or part or all of them are deuterium; R, R' and R" are each independently hydrogen or deuterium, n1 to n2 are each independently an integer of 0 to 4, and n3 is an integer of 0 to 2; Ar1, Ar2 are each independently a substituted or unsubstituted aryl or heteroaryl group; and

[0009] provided that the compound is not the following molecule:

[0010]

[0011] 2) The triarylamine-based compound for an organic electroluminescent device according to 1), wherein R2or R3is a carbazolyl group.

[0012] 3) The triarylamine-based compound for an organic electroluminescent device according to 1), wherein Ar1and Ar2are each independently a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring-forming atoms, the heteroaryl group containing one or more of O, N, and S as a heteroatom.

[0013] 4) The triarylamine-based compound for an organic electroluminescent device according to 1), wherein Ar1and Ar2are each independently selected from the group consisting of a substituted or unsubstituted thienyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted indenofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted carbazolyl group.

[0014] 5) The triarylamine-based compound for an organic electroluminescent device according to 1), wherein the triarylamine-based compound is selected from the group consisting of the following structures:

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036] 6) An organic electroluminescent device, wherein the organic electroluminescent device comprises an anode, a cathode, and at least one organic thin film located between the anode and the cathode, the organic thin film containing any one of the compounds described in 1) to 5).

[0037] 7) The organic electroluminescent device according to 6), wherein the compound is used as an electron blocking material or a hole transport material in the organic electroluminescent device.

[0038] Compared with the prior art, the beneficial effects of the present invention are: effectively suppressing molecular aggregation, thereby forming a stable and dense thin film; effectively regulating the energy level barrier and hole mobility, improving the efficiency and lifetime of the device; and more effectively suppressing the diffusion of electrons from the light-emitting layer to the hole side, thereby improving the lifetime of the device. Attached Figure Description

[0039] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings:

[0040] Figure 1 The diagram below shows the structure of an organic electroluminescent device using the compounds of this invention. The meanings of each layer in the device are as follows:

[0041] 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. Detailed Implementation

[0042] The principles and features of the present invention will be further illustrated below with several synthetic and device embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, the types of isotopes of hydrogen atoms present within the molecules of the compounds used in this invention are not particularly limited; for example, all hydrogen atoms within the molecule may be... 1 H can be partially or entirely... 2 H(deuterium)D).

[0043] Synthesis Example 1

[0044] Synthesis of intermediate M1-1:

[0045]

[0046] 2,4-Difluorobromobenzene (RM-1, 5.0 g, 25.9 mmol), carbazole (RM-2, 17.3 g, 103.6 mmol), cesium carbonate (42.2 g, 129.5 mmol), and 100 mL of N,N-dimethylformamide (DMF) were added to a 250 mL three-necked flask, and the mixture was purged with nitrogen three times. The reaction was carried out overnight at 150 °C under nitrogen protection. After the reaction was complete, 100 mL of deionized water was added, and the mixture was stirred at room temperature for 1 h. The mixture was filtered, and the filter cake was slurried with acetone to remove excess carbazole. Recrystallization from toluene and methanol yielded 8.94 g of a white solid, with a yield of 71%; the molecular weight was determined by liquid chromatography-mass spectrometry to be m / z = 486.12.

[0047] Synthesis of intermediate M1-2:

[0048]

[0049] Intermediate M1-1 (3.0 g, 6.2 mmol), p-chlorophenylboronic acid (RM-3, 1.16 g, 7.42 mmol), tetrakis(triphenylphosphine)palladium (0.30 g, 0.25 mmol), potassium carbonate (1.70 g, 12.4 mmol), 30 mL of toluene, and 6 mL of water were added. The reaction mixture was purged three times under nitrogen protection. Under nitrogen protection, the mixture was heated and stirred, and refluxed at 110 °C for 12 h. The reaction was stopped, cooled to room temperature, and 100 mL of deionized water was added. The mixture was extracted three times with dichloromethane. The solution was dried over anhydrous sodium sulfate, and the filtrate was concentrated. Recrystallization from methanol and toluene yielded 2.12 g of a white solid, with a yield of 66%; the molecular weight was determined to be m / z = 518.12 by liquid chromatography-mass spectrometry.

[0050]

[0051] Synthesis of compound EB002:

[0052] Intermediate Ml-2 (2.12 g, 4.1 mmol), diphenylamine (Nl, 0.66 g, 3.9 mmol), tris(dibenzylideneacetone)dipalladium (0.14 g, 0.15 mmol), sodium tert-butoxide (0.77 g, 8 mmol). The reaction system was replaced with nitrogen three times. A needle tube was used to add (0.6 mL, 0.6 mmol) a toluene solution (1 mol / L) of tri-tert-butylphosphine and 10 mL of toluene. Under nitrogen protection, heating and stirring were carried out, and the reaction was refluxed at 120°C for 12 h. The reaction was stopped, cooled to room temperature, 50 mL of deionized water was added, and extracted with ethyl acetate three times. Anhydrous sodium sulfate was used for drying, and the filtrate was concentrated. Silica gel column separation, dichloromethane / petroleum ether (1:4) elution, and solvent evaporation. Recrystallization with methanol and toluene to obtain 1.83 g of white solid, yield 72%; liquid chromatography-mass spectrometry showed that the molecular weight was m / z = 651.17.

[0053] Synthesis Example 2

[0054] Synthesis of intermediate M2-1:

[0055]

[0056] 2,3-difluorobromobenzene (RM-4, 5.0 g, 25.9 mmol), carbazole (RM-2, 17.3 g, 103.6 mmol), cesium carbonate (42.2 g, 129.5 mmol) and 100 mL of N,N-dimethylformamide (DMF) were added to a 250 mL three-necked flask, and nitrogen was replaced three times. Under nitrogen protection, the reaction was carried out at 150°C overnight. After the reaction was completed, 100 mL of deionized water was added, and stirred at room temperature for 1 h. Filtration, and the filter cake was washed with acetone to remove excess carbazole. Recrystallization with toluene and methanol to obtain 8.62 g of white solid, yield 68%; liquid chromatography-mass spectrometry showed that the molecular weight was m / z = 486.15;

[0057] Synthesis of intermediate M2-2:

[0058]

[0059] Intermediate M2-1 (3.0 g, 6.2 mmol), p-chlorobenzeneboronic acid (RM-3, 1.16 g, 7.42 mmol), tetrakis(triphenylphosphine)palladium (0.30 g, 0.25 mmol), potassium carbonate (1.70 g, 12.4 mmol), 30 mL of toluene and 6 mL of water were added to the reaction system, which was purged with nitrogen three times. The reaction was heated and stirred under nitrogen protection at 110 °C for 12 h. The reaction was stopped and cooled to room temperature, 100 mL of deionized water was added, and the mixture was extracted with dichloromethane three times. The filtrate was dried over anhydrous sodium sulfate and concentrated. Recrystallization was performed with methanol and toluene to obtain 2.15 g of white solid with a yield of 68%; the molecular weight of the compound EB005 was determined by liquid chromatography-mass spectrometry to be m / z = 518.13; synthesis of compound EB005:

[0060]

[0061] Intermediate M2-2 (2.12 g, 4.1 mmol), N2 (0.96 g, 3.9 mmol), tris(dibenzylideneacetone)dipalladium (0.14 g, 0.15 mmol), sodium tert-butoxide (0.77 g, 8 mmol) were added to the reaction system, which was purged with nitrogen three times. A needle tube was used to add (0.6 mL, 0.6 mmol) of a toluene solution (1 mol / L) of tri-tert-butylphosphine and 10 mL of toluene. The reaction was heated and stirred under nitrogen protection at 120 °C for 12 h. The reaction was stopped and cooled to room temperature, 50 mL of deionized water was added, and the mixture was extracted with ethyl acetate three times. The filtrate was dried over anhydrous sodium sulfate and concentrated. The filtrate was separated on a silica gel column eluted with dichloromethane / petroleum ether (1:5) and the solvent was rotary evaporated. Recrystallization was performed with methanol and toluene to obtain 2.01 g of white solid with a yield of 71%; the molecular weight of the compound EB005 was determined by liquid chromatography-mass spectrometry to be m / z = 727.32.

[0062] Synthesis Example 3

[0063] Synthesis of intermediate M3-1:

[0064]

[0065] 2,6-difluorobromobenzene (RM-5, 5.0 g, 25.9 mmol), carbazole (RM-2, 17.3 g, 103.6 mmol), cesium carbonate (42.2 g, 129.5 mmol) and 100 mL of N,N-dimethylformamide (DMF) were added to a 250 mL three-necked flask, which was purged with nitrogen three times. The reaction was carried out under nitrogen protection at 150 °C overnight. After the reaction was completed, 100 mL of deionized water was added and stirred at room temperature for 1 h. Filtration was performed and the filter cake was slurried with acetone to remove excess carbazole. Recrystallization was performed with toluene and methanol to obtain 9.20 g of white solid with a yield of 73%; the molecular weight of the compound EB005 was determined by liquid chromatography-mass spectrometry to be m / z = 486.15;

[0066] Synthesis of intermediate M3-2:

[0067]

[0068] Intermediate M3-1 (3.0 g, 6.2 mmol), p-chlorobenzeneboronic acid (RM-3, 1.16 g, 7.42 mmol), tetrakis(triphenylphosphine)palladium (0.30 g, 0.25 mmol), potassium carbonate (1.70 g, 12.4 mmol), 30 mL of toluene and 6 mL of water were added to the reaction system, which was degassed three times with nitrogen protection. The reaction was heated and stirred under nitrogen protection at 110 °C for 12 h. The reaction was stopped and cooled to room temperature, 100 mL of deionized water was added, and the mixture was extracted three times with dichloromethane. The filtrate was dried over anhydrous sodium sulfate and concentrated. Recrystallization with methanol and toluene gave 2.16 g of white solid with a yield of 67%; the molecular weight of the compound EB012 was m / z = 518.13 by liquid chromatography-mass spectrometry; and the synthesis of compound EB012:

[0069]

[0070] Intermediate M3-2 (2.12 g, 4.1 mmol), N3 (1.15 g, 3.9 mmol), tris(dibenzylideneacetone)dipalladium (0.14 g, 0.15 mmol), sodium tert-butoxide (0.77 g, 8 mmol) were added to the reaction system, which was degassed three times with nitrogen protection. A needle tube was used to add (0.6 mL, 0.6 mmol) of a toluene solution (1 mol / L) of tri-tert-butylphosphine and 10 mL of toluene. The reaction was heated and stirred under nitrogen protection at 120 °C for 12 h. The reaction was stopped and cooled to room temperature, 50 mL of deionized water was added, and the mixture was extracted three times with ethyl acetate. The filtrate was dried over anhydrous sodium sulfate and concentrated. The product was separated by silica gel column chromatography, eluted with dichloromethane / petroleum ether (1:5), and the solvent was rotary evaporated. Recrystallization with methanol and toluene gave 2.01 g of white solid with a yield of 71%; the molecular weight of the compound EB012 was m / z = 777.32 by liquid chromatography-mass spectrometry.

[0071] Synthesis Example 4

[0072] Synthesis of intermediate M4-1:

[0073]

[0074] 2,5-Difluorobromobenzene (RM-6, 5.0 g, 25.9 mmol), carbazole (RM-2, 17.3 g, 103.6 mmol), cesium carbonate (42.2 g, 129.5 mmol), and 100 mL of N,N-dimethylformamide (DMF) were added to a 250 mL three-necked flask, and the mixture was purged with nitrogen three times. The reaction was carried out overnight at 150 °C under nitrogen protection. After the reaction was complete, 100 mL of deionized water was added, and the mixture was stirred at room temperature for 1 h. The mixture was filtered, and the filter cake was slurried with acetone to remove excess carbazole. Recrystallization from toluene and methanol yielded 9.45 g of a white solid, 75% yield; the molecular weight was determined by liquid chromatography-mass spectrometry to be m / z = 486.15.

[0075] Synthesis of intermediate M4-2:

[0076]

[0077] Intermediate M4-1 (3.0 g, 6.2 mmol), p-chlorophenylboronic acid (RM-3, 1.16 g, 7.42 mmol), tetrakis(triphenylphosphine)palladium (0.30 g, 0.25 mmol), potassium carbonate (1.70 g, 12.4 mmol), 30 mL of toluene, and 6 mL of water were added. The reaction system was purged three times under nitrogen protection. Under nitrogen protection, the mixture was heated and stirred, and refluxed at 110 °C for 12 h. The reaction was stopped, cooled to room temperature, and 100 mL of deionized water was added. The mixture was extracted three times with dichloromethane. The solution was dried over anhydrous sodium sulfate, and the filtrate was concentrated. Recrystallization from methanol and toluene yielded 2.19 g of a white solid, with a yield of 68%. The molecular weight was determined by liquid chromatography-mass spectrometry to be m / z = 518.13. Synthesis of compound EB016:

[0078]

[0079] Intermediate M4-2 (2.12 g, 4.1 mmol), N4 (1.15 g, 3.9 mmol), tris(dibenzylacetone)dipalladium (0.14 g, 0.15 mmol), and sodium tert-butoxide (0.77 g, 8 mmol) were added. The reaction system was purged three times under nitrogen protection. Then, a 1 mol / L solution of tri-tert-butylphosphine in toluene (0.6 mL, 0.6 mmol) and 10 mL of toluene were added via syringe. Under nitrogen protection, the mixture was heated and stirred, and refluxed at 120 °C for 12 h. The reaction was stopped, cooled to room temperature, and 50 mL of deionized water was added. The mixture was extracted three times with ethyl acetate. The solution was dried over anhydrous sodium sulfate, and the filtrate was concentrated. Separation was performed by silica gel column chromatography, followed by elution with dichloromethane / petroleum ether (1:5), and the solvent was evaporated to dryness. Recrystallization from methanol and toluene yielded 2.04 g of a white solid, 72% yield; the molecular weight was determined to be m / z = 777.32 by liquid chromatography-mass spectrometry.

[0080] Synthesis Example 5

[0081] Synthesis of compound EB026:

[0082]

[0083] Synthesis of compound EB026 was the same as example 1 except that compound N5 was used instead of compound N1 in the preparation of example 5. Recrystallization gave a white solid with a yield of 73%. The molecular weight was measured by liquid mass spectrometry as m / z = 777.28.

[0084] Synthesis of example 6

[0085] Synthesis of compound EB031:

[0086]

[0087] Synthesis of compound EB031 was the same as example 4 except that compound N6 was used instead of compound N4 in the preparation of example 6. Recrystallization gave a white solid with a yield of 73%. The molecular weight was measured by liquid mass spectrometry as m / z = 827.35.

[0088] Synthesis of example 7

[0089] Synthesis of compound EB040:

[0090]

[0091] Synthesis of compound EB040 was the same as example 3 except that compound N7 was used instead of compound N3 in the preparation of example 7. Recrystallization gave a white solid with a yield of 71%. The molecular weight was measured by liquid mass spectrometry as m / z = 803.19.

[0092] Synthesis of example 8

[0093] Synthesis of compound EB046:

[0094]

[0095] Synthesis of compound EB046 was the same as example 1 except that compound N8 was used instead of compound N1 in the preparation of example 8. Recrystallization gave a white solid with a yield of 75%. The molecular weight was measured by liquid mass spectrometry as m / z = 803.23.

[0096] Synthesis of example 9

[0097] Synthesis of compound EB051:

[0098]

[0099] The synthesis of compound EB051 was the same as example 4 except that compound N9 was used instead of compound N4 during the preparation of example 9. Recrystallization gave a white solid in 74% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 803.27.

[0100] Synthesis of example 10

[0101] Synthesis of compound EB061:

[0102]

[0103] The synthesis of compound EB061 was the same as example 2 except that compound N10 was used instead of compound N2 during the preparation of example 10. Recrystallization gave a white solid in 71% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 879.37.

[0104] Synthesis of example 11

[0105] Synthesis of compound EB070:

[0106]

[0107] The synthesis of compound EB070 was the same as example 1 except that compound N11 was used instead of compound N1 during the preparation of example 11. Recrystallization gave a white solid in 72% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 853.37.

[0108] Synthesis of example 12

[0109] Synthesis of compound EB083:

[0110]

[0111] The synthesis of compound EB083 was the same as example 4 except that compound N12 was used instead of compound N4 during the preparation of example 12. Recrystallization gave a white solid in 69% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 903.32.

[0112] Synthesis of example 13

[0113] Synthesis of compound EB086:

[0114]

[0115] The synthesis of compound EB086 was carried out as in example 1 except that compound N13 was used instead of compound N1 during the preparation of example 13. Recrystallization gave a white solid in 74% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 903.25.

[0116] Synthesis of example 14

[0117] Synthesis of compound EB096:

[0118]

[0119] The synthesis of compound EB096 was carried out as in example 3 except that compound N14 was used instead of compound N3 during the preparation of example 14. Recrystallization gave a white solid in 72% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 853.27.

[0120] Synthesis of example 15

[0121] Synthesis of compound EB101:

[0122]

[0123] The synthesis of compound EB101 was carried out as in example 2 except that compound N15 was used instead of compound N2 during the preparation of example 15. Recrystallization gave a white solid in 74% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 767.31.

[0124] Synthesis of example 16

[0125] Synthesis of compound EB122:

[0126]

[0127] The synthesis of compound EB122 was carried out as in example 1 except that compound N16 was used instead of compound N1 during the preparation of example 16. Recrystallization gave a white solid in 71% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 893.27.

[0128] Synthesis of example 17

[0129] Synthesis of compound EB154:

[0130]

[0131] The synthesis of compound EB154 was the same as example 1 except that compound N17 was used instead of compound N1 during the preparation of example 17. Recrystallization gave a white solid in 73% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 857.28.

[0132] Synthesis of example 18

[0133] Synthesis of compound EB166:

[0134]

[0135] The synthesis of compound EB166 was the same as example 1 except that compound N18 was used instead of compound N1 during the preparation of example 18. Recrystallization gave a white solid in 71% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 893.29.

[0136] Synthesis of example 19

[0137] Synthesis of compound EB198:

[0138]

[0139] The synthesis of compound EB198 was the same as example 1 except that compound N19 was used instead of compound N1 during the preparation of example 19. Recrystallization gave a white solid in 75% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 893.28.

[0140] Synthesis of example 20

[0141] Synthesis of compound EB199:

[0142]

[0143] The synthesis of compound EB199 was the same as example 1 except that compound N19 was used instead of compound N1 during the preparation of example 20. Recrystallization gave a white solid in 71% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 893.24.

[0144] Synthesis of example 21

[0145] Synthesis of compound EB228:

[0146]

[0147] Synthesis of compound EB228 was the same as example 3 except that compound N20 was used instead of compound N3 during the preparation of example 21. Recrystallization gave a white solid in 70% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 893.25.

[0148] Synthesis of example 22

[0149] Synthesis of compound EB227:

[0150]

[0151] Synthesis of compound EB227 was the same as example 2 except that compound N21 was used instead of compound N2 during the preparation of example 22. Recrystallization gave a white solid in 73% yield. The molecular weight was measured by liquid mass spectrometry as m / z = 893.22.

[0152] Synthesis of example 23

[0153] Synthesis of compound EB247:

[0154]

[0155] Synthesis of compound EB247 was the same as example 1 except that compounds RM-7 and N8 were used instead of compounds RM-1 and N1, respectively, during the preparation of example 23. Recrystallization gave a white solid. The molecular weight was measured by liquid mass spectrometry as m / z = 879.31.

[0156] Synthesis of example 24

[0157] Synthesis of compound EB250:

[0158]

[0159] Synthesis of compound EB250 was the same as example 1 except that compounds RM-8 and N8 were used instead of compounds RM-1 and N1, respectively, during the preparation of example 24. Recrystallization gave a white solid. The molecular weight was measured by liquid mass spectrometry as m / z = 807.32.

[0160] Synthesis of example 25

[0161] Synthesis of compound EB254:

[0162]

[0163] Synthesis of compound EB254 was the same as example 1 except that compound RM-9 and N8 were used instead of compounds RM-1 and N1, respectively, during the preparation of example 25. Recrystallization gave a white solid with a mass of m / z = 806.29 by liquid chromatography mass spectrometry.

[0164] Synthesis of example 26

[0165] Synthesis of compound EB258:

[0166]

[0167] Synthesis of compound EB258 was the same as example 1 except that compound RM-10 and N8 were used instead of compounds RM-1 and N1, respectively, during the preparation of example 26. Recrystallization gave a white solid with a mass of m / z = 818.39 by liquid chromatography mass spectrometry.

[0168] Synthesis of example 27

[0169] Synthesis of compound EB271:

[0170]

[0171] Synthesis of compound EB271 was the same as example 1 except that compound N22 was used instead of compound N1 during the preparation of example 27. Recrystallization gave a white solid with a yield of 72%. The mass was m / z = 821.38 by liquid chromatography mass spectrometry.

[0172] Synthesis of example 28

[0173] Synthesis of compound EB301:

[0174]

[0175] Synthesis of compound EB301 was the same as example 1 except that compounds RM-9, RM-10, RM-8, and N11 were used instead of compounds RM-1, RM-2, RM-3, and N1, respectively, during the preparation of example 28. Recrystallization gave a white solid with a mass of m / z = 876.42 by liquid chromatography mass spectrometry.

[0176] Synthesis of example 29

[0177] Synthesis of compound EB310:

[0178]

[0179] Synthesis of compound EB310 was the same as example 1 except that compound RM-9, RM-10, RM-8 and N22 were used instead of compound RM-1, RM-2, RM-3 and N1, respectively, in the preparation of example 29. Recrystallization gave a white solid with a mass of m / z = 876.42 by liquid mass spectrometry.

[0180] Synthesis of example 30

[0181] Synthesis of compound EB316:

[0182]

[0183] Synthesis of compound EB316 was the same as example 3 except that compound RM-11 and N2 were used instead of compound RM-3 and N3, respectively, in the preparation of example 30. Recrystallization gave a white solid with a mass of m / z = 727.32 by liquid mass spectrometry.

[0184] Synthesis of example 31

[0185] Synthesis of compound EB313:

[0186]

[0187] Synthesis of compound EB313 was the same as example 2 except that compound RM-11 was used instead of compound RM-3 in the preparation of example 31. Recrystallization gave a white solid with a mass of m / z = 727.33 by liquid mass spectrometry.

[0188] Synthesis of example 32

[0189] Synthesis of compound EB330:

[0190]

[0191] Synthesis of compound EB330 was the same as example 1 except that compound RM-11 and N11 were used instead of compound RM-3 and N1, respectively, in the preparation of example 32. Recrystallization gave a white solid with a mass of m / z = 853.27 by liquid mass spectrometry.

[0192] Synthesis of example 33

[0193] Synthesis of compound EB343:

[0194]

[0195] Synthesis of compound EB343 was the same as example 4 except that compound RM-11 and N19 were used instead of compound RM-3 and N1 respectively during the preparation of example 33. Recrystallization gave a white solid with a mass of m / z = 893.27 by liquid chromatography mass spectrometry.

[0196] Synthesis of example 34

[0197] Synthesis of compound EB354:

[0198]

[0199] Synthesis of compound EB354 was the same as example 1 except that compound RM-11 and N12 were used instead of compound RM-3 and N1 respectively during the preparation of example 33. Recrystallization gave a white solid with a mass of m / z = 903.26 by liquid chromatography mass spectrometry.

[0200] Synthesis of example 35

[0201] Synthesis of compound EB380:

[0202]

[0203] Synthesis of compound EB380 was the same as example 2 except that compound RM-11 and N23 were used instead of compound RM-3 and N3 respectively during the preparation of example 35. Recrystallization gave a white solid with a mass of m / z = 843.31 by liquid chromatography mass spectrometry.

[0204] Synthesis of example 36

[0205] Synthesis of compound EB382:

[0206]

[0207] Synthesis of compound EB382 was the same as example 1 except that compound RM-12 and N8 were used instead of compound RM-3 and N1 respectively during the preparation of example 36. Recrystallization gave a white solid with a mass of m / z = 807.25 by liquid chromatography mass spectrometry.

[0208] Synthesis of example 37

[0209] Synthesis of compound EB387:

[0210]

[0211] The synthesis of compound EB387 was the same as example 4, except that compounds RM9, RM-11 and N8 were used instead of compounds RM-4, RM-3 and N4, respectively, in the preparation of example 37. Recrystallization gave a white solid, and the molecular weight was measured by liquid chromatography mass spectrometry to be m / z = 806.26.

[0212] Synthesis of example 38

[0213] Synthesis of compound EB390:

[0214]

[0215] The synthesis of compound EB390 was the same as example 1, except that compounds RM-9, RM-10, RM-12 and N8 were used instead of compounds RM-1, RM-2, RM-3 and N1, respectively, in the preparation of example 38. Recrystallization gave a white solid, and the molecular weight was measured by liquid chromatography mass spectrometry to be m / z = 826.35.

[0216] Synthesis of example 39

[0217] Synthesis of compound EB402:

[0218]

[0219] The synthesis of compound EB402 was the same as example 1, except that compounds RM-9, RM-10, RM-12 and N22 were used instead of compounds RM-1, RM-2, RM-3 and N1, respectively, in the preparation of example 36. Recrystallization gave a white solid, and the molecular weight was measured by liquid chromatography mass spectrometry to be m / z = 844.54.

[0220] Device example: fabrication of an organic electroluminescent device for use as an electron blocking layer material

[0221] A 30 mm x 30 mm x 1.1 mm thick glass substrate with an indium tin oxide (ITO) transparent electrode (anode) was ultrasonically cleaned in isopropanol for 5 minutes, and then subjected to ultraviolet (UV)-ozone cleaning for 30 minutes. The cleaned glass substrate was mounted on a substrate holder of a vacuum vapor deposition apparatus, and vacuumed to 1 x 10 -5 ~ 1 x 10 -6Pa, HATCN hole injection layer (HIL) was evaporated on the ITO transparent electrode, film thickness 15 nm. On the hole injection layer, HT was evaporated as hole transport layer (HTL), film thickness 60 nm. Then, on the hole transport layer, EB005 was evaporated as electron blocking layer (EBL), film thickness 10 nm. Then, on the electron blocking layer, the light emitting layer (EML) was co-evaporated, film thickness 20 nm; the light emitting layer (EML) was co-evaporated by using multi-source co-evaporation method to evaporate the host material and the light emitting material (BH and BD) of the light emitting layer, wherein the doping concentration of the light emitting material was 2%wt. Then, on the light emitting layer, HB was evaporated as hole blocking layer (HBL), film thickness 5 nm. Then, on the hole blocking layer, 1:1 co-evaporated electron transport material (ET) and 8-hydroxyquinoline lithium (Liq) as electron transport layer (ETL), film thickness 30 nm. In addition, Liq was evaporated on the ETL as electron injection layer (EIL), film thickness 1 nm. Then, on the EIL, metal cathode aluminum (Al) was evaporated, film thickness 100 nm. The structure of the organic electroluminescent device of Example 1 is shown in Figure 1 Figure 1 The superimposed order and the role of each functional layer are also shown.

[0222] The OLED in principle has the following layer structure: ITO substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / light emitting layer (EML) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) and finally cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. The exact structure of the OLED is shown in Table 1.

[0223] Table 1 Materials for OLED

[0224]

[0225] Device Example 1:

[0226] ITO (130) / HATCN 15) / HT (60) / EB005 (10) / BH:BD (20, 2%wt) / HB (5) / ET:Liq (30, 50%wt) / Liq (1) / Al (100)

[0227] Device Examples 2-26 differ from Device Example 1 only in that the EB005 used in the electron blocking layer is replaced by other compounds of the present application, and the performance test data of the resulting devices are shown in Table 2.

[0228] Comparative Examples 1-3:

[0229] ​The comparative example differs from device example 1 in that EB005 in the organic electroluminescent device is changed to EB-1, EB-2, EB-3 which are well known in the industry and have been commercially applied. The performance test data of the obtained devices are shown in Table 2.

[0230] The OLEDs were characterized by standard methods. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in %) were determined as a function of the luminous density from the current / voltage / luminous density characteristic (IUL characteristic) which exhibits a Lambertian emission characteristic. The voltage V1000 required at a luminance of 1000 cd / m 2 The CE1000 represents the current efficiency achieved at 1000 cd / m 2 The EQE1000 represents the external quantum efficiency at an operating luminance of 1000 cd / m 2 The T95 represents the operating time until the luminance of the device has decreased to 95% at an initial luminance of 1000 cd / m 2

[0231] The device performance of examples 1 to 26 and comparative examples 1 to 3 of the present application is summarized in Table 2:

[0232] Table 2: Overview of device performance

[0233]

[0234]

[0235] ​As can be seen from Table 2, compared with the prior art, using the material examples 1-26 of the present application, the device efficiency can be slightly improved and the device lifetime can be greatly improved while maintaining the driving voltage of the OLED. As in device example 4 of EB046, the CE1000 is compared with comparative example 2, the efficiency is improved by 6.8%, and the lifetime is improved by 12.3%. While the CE1000 of device example 17 of EB310 is compared with comparative example 2, the efficiency is improved by 5.7%, and the lifetime is greatly improved by 56.7%. In the EBL, a carbazole unit is usually used as a unit for adjusting the energy level, and by introducing a double carbazole unit, the present application adjusts the mobility of the material while the carbazole unit regulates the energy level of the material, ensuring that the transmission of electrons and holes in the entire device is more balanced, thereby slightly improving the device efficiency and greatly improving the device lifetime while maintaining the driving voltage of the OLED. Secondly, by comparing EB046, EB250, EB258 and EB310, it can be seen that replacing the hydrogen (H) atoms in the material of the present application with deuterium (D) atoms partially or completely, the lifetime will be significantly improved, and the improvement ratio will increase with the increase of the deuterium substitution rate; the reason is that the C-D bond is shorter than the C-H bond, so that the C-D bond is more stable than the C-H bond, thereby improving the lifetime of the device.

Claims

1. A triarylamine compound for use in organic electroluminescent devices, characterized in that, The compound is represented by formula (1): In this configuration, one of R1 to R4 is a carbazoyl group, and the rest are each independently hydrogen or deuterium, wherein all hydrogen atoms on the carbazoyl group are hydrogen, or partially or entirely deuterium; R, R', and R” are each independently hydrogen or deuterium; n1 to n2 are each independently an integer from 0 to 4; and n3 is an integer from 0 to 2. Ar1 and Ar2 are each independently selected from: unsubstituted phenyl, unsubstituted biphenyl, unsubstituted fluorenyl, unsubstituted dibenzothiophene, and unsubstituted dibenzofuranyl.

2. The triarylamine compound for organic electroluminescent devices according to claim 1, characterized in that, R2 or R3 is a carbazole group.

3. A triarylamine compound for use in organic electroluminescent devices, characterized in that, The triarylamine compounds are selected from the following structures:

4. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and at least one organic thin film located between the anode and the cathode, wherein the organic thin film contains the compound according to any one of claims 1 to 3, and the compound is used as an electron blocking material or a hole transport material in the organic electroluminescent device.

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