Olefin functional group carbazole derivative and application thereof
Patent Information
- Application Number
- CN202510394675.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-31
- Publication Date
- 2025-07-29
Smart Images
Figure CN120383550A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of organic optoelectronics, and particularly relates to an olefin-functionalized carbazole derivative and its application. Background Art
[0002] Organic light-emitting devices (OLEDs) have broad application prospects in the fields of new displays, lighting, sensing, medical treatment, etc. In particular, as the display screen of current high-end smartphones, they have been popularized and applied, and the demand for iterative upgrading of related technologies is becoming more urgent.
[0003] Vacuum evaporation is the preparation process of current commercial OLEDs. However, due to high costs, material waste, difficulty in achieving large-area, rapid, and low-cost preparation, especially the metal mask plates required for the evaporation process are limited by size, it is difficult to prepare ultra-high-resolution displays and cannot meet the application requirements of scenarios such as virtual reality. The semiconductor devices prepared by solution processing technology require mild conditions, low energy consumption, and low cost, are suitable for the preparation of large-scale semiconductor devices, and can combine photolithography technology to achieve the preparation of ultra-high-resolution array films. However, due to the problem that the organic layer is easily dissolved by organic solvents, it is difficult to directly and continuously prepare multi-layer films based on the solution method. The photo-crosslinking method can make the crosslinked material become insoluble after crosslinking, which can solve the erosion problem caused by the use of solvents during the preparation between layers; at the same time, the crosslinkable luminescent material combined with direct photolithography technology can achieve high-resolution patterning, with a short process time, which is beneficial to realizing an ultra-high-resolution full-color display array and has important application prospects. Summary of the Invention
[0004] The purpose of the present invention is to overcome the deficiencies of the prior art and provide an olefin-functionalized carbazole derivative and its application.
[0005] According to one aspect of the present invention, an olefin-functionalized carbazole derivative is provided, and the structural formula of the olefin-functionalized carbazole derivative is shown as follows:
[0006]
[0007] Among them, R1 is selected from any one of the following structures:
[0008]
[0009] R2 is selected from any one of vinyl, styryl, vinyl ether, acrylate group, methyl(vinyl) silanediamine, norbornene, maleimide, and methyl acrylate group.
[0010] Furthermore, the structural formula of the olefin-functionalized carbazole derivative is any one of the following formulas 1 to 28:
[0011]
[0012]
[0013]
[0014]
[0015]
[0016] According to the second aspect of the present invention, an organic electroluminescent material is provided, which includes the olefin-functionalized carbazole derivative as described above. Specifically, the organic electroluminescent material includes a thin film structure, which is prepared by mixing the olefin-functionalized carbazole derivative with a thiol crosslinking agent and then performing a photocrosslinking reaction.
[0017] Further, the thiol crosslinking agent is pentaerythritol tetra(3-mercaptopropionate), and the mass ratio of the olefin-functionalized carbazole derivative to the thiol crosslinking agent is (8-15):1, such as 8:1, 10:1, 12:1, 15:1 or any value therebetween.
[0018] Further, the ultraviolet light irradiation wavelength range for the photocrosslinking reaction is 250 nm to 400 nm, such as 250 nm, 300 nm, 350 nm, 400 nm or any value therebetween, and the time for the photocrosslinking reaction is 30 seconds to 300 seconds, such as 30 seconds, 60 seconds, 90 seconds, 120 seconds, 150 seconds, 180 seconds, 210 seconds, 240 seconds, 270 seconds, 300 seconds or any value therebetween.
[0019] Further, the organic electroluminescent material is used as a hole transport layer and / or a light-emitting layer of an organic electroluminescent device.
[0020] According to the third aspect of the present invention, an organic electroluminescent device is provided, which includes a cathode layer, an anode layer, and an organic layer between the cathode layer and the anode layer, and the organic layer contains the olefin-functionalized carbazole derivative or its product.
[0021] Further, after the olefin-functionalized carbazole derivative is mixed with the thiol crosslinking agent, a thin film structure is formed by a photocrosslinking reaction for use in the organic electroluminescent device.
[0022] Further, the thiol crosslinking agent is pentaerythritol tetra(3-mercaptopropionate), and the mass ratio of the olefin-functionalized carbazole derivative to the thiol crosslinking agent is (8-15):1, such as 8:1, 10:1, 12:1, 15:1 or any value therebetween. The ultraviolet light wavelength range for the photocrosslinking reaction is 250 nanometers to 400 nanometers, such as 250 nanometers, 300 nanometers, 350 nanometers, 400 nanometers or any value therebetween. The time for the photocrosslinking reaction is 30 seconds to 300 seconds, such as 30 seconds, 60 seconds, 90 seconds, 120 seconds, 150 seconds, 180 seconds, 210 seconds, 240 seconds, 270 seconds, 300 seconds or any value therebetween.
[0023] According to the fourth aspect of the present invention, an application of the olefin-functionalized carbazole derivative is proposed. The application is as a functional material in an organic electronic device, and the organic electronic device is selected from an organic light-emitting device, an organic solar cell, an organic thin-film transistor, a perovskite solar cell or a perovskite light-emitting diode.
[0024] Advantages of the present invention:
[0025] The olefin-functionalized carbazole derivative provided by the present invention has a carbazole benzene as the core, is connected with different carrier transport groups or light-emitting groups, and then is coupled with different olefin functional groups. The olefin-functionalized carbazole derivative has a relatively high triplet energy level, which is beneficial to confining excitons in the light-emitting layer, thereby improving the light-emitting efficiency. In addition, the olefin-functionalized carbazole derivative is suitable for preparing a hole transport layer or a light-emitting layer material of an organic light-emitting device. Mainly through the thiol-olefin click reaction occurring between the olefin-functionalized carbazole derivative and the thiol crosslinking agent, a three-dimensional crosslinked network is formed, making the material have good solvent resistance. Moreover, when the olefin-functionalized carbazole derivative of the present invention is applied to an organic light-emitting device, the light-emitting efficiency and service life of the organic light-emitting device can be effectively improved. In addition, the olefin-functionalized carbazole derivative of the present invention can also be applied to fields such as organic solar cells, organic thin-film transistors, perovskite solar cells and perovskite light-emitting diodes, and has broad application potential. Description of the Drawings
[0026] Figure 1 Shows the photophysical property result graph of the toluene solution of the olefin-functionalized carbazole derivative in a specific embodiment according to the present invention;
[0027] Figure 2 Shows the solvent resistance property test result graph of the olefin-functionalized carbazole derivative in a specific embodiment according to the present invention;
[0028] Figure 3The figure shows the test results of the electroluminescence performance of the organic electroluminescent device described in a specific embodiment of the present invention. Detailed Description of the Invention
[0029] The present application will be further described in detail below with reference to the accompanying drawings and embodiments. It can be understood that the specific embodiments described herein are only for explaining the related invention and not for limiting the invention. Additionally, it should be noted that for the convenience of description, only the parts related to the invention are shown in the drawings.
[0030] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present application will be described in detail below with reference to the drawings and embodiments.
[0031] The first object of the present invention is to provide an olefin-functionalized carbazole derivative, which has a relatively high triplet energy level, can be beneficial to confine excitons in the light-emitting layer, and thus improve the luminous efficiency.
[0032] In view of the deficiencies such as the easy dissolution of the organic layer of the current organic electroluminescent device during the preparation process, the second object of the present invention is to provide an organic electroluminescent material, which is prepared based on a photocrosslinking method and has good solvent resistance.
[0033] The third object of the present invention is to provide an organic electroluminescent device, the luminous efficiency and service life of which are effectively improved.
[0034] The fourth object of the present invention is to provide an application of the olefin-functionalized carbazole derivative, which can be used to prepare functional materials in organic electronic devices and has broad application potential.
[0035] The olefin-functionalized carbazole derivative provided by the present invention takes carbazole benzene as the core, connects different charge transport groups or light-emitting groups, and then couples different olefin functional groups. The structural formula of the olefin-functionalized carbazole derivative is shown as follows:
[0036]
[0037] Among them, R1 is selected from any one of the following structures:
[0038]
[0039] R2 is selected from any one of vinyl, styryl, vinyl ether, acrylate group, methyl(vinyl)silanediamine, norbornene, maleimide, and methyl acrylate group.
[0040] The structural formula of the olefin-functionalized carbazole derivative is any one of the following formulas 1 to 28:
[0041]
[0042]
[0043]
[0044]
[0045]
[0046] Although the following specific examples are described with Compound 1 as the selected type, these examples are equally applicable to the selected types listed above and other unlisted ones. With reference to the accompanying drawings, the process, steps and result analysis of the specific implementation of the present invention are as follows:
[0047] Example 1: Synthesis of Compound 1
[0048] Compound 1 was synthesized according to the following experimental steps:
[0049] (1) Synthesis of 9,9'-([1,1'-biphenyl]-3,5-diyl)bis(9H-carbazole-4-methoxy): 1644 mg (3 mmol) of 9,9'-(5-bromo-1,3-phenylene)bis(4-methoxy-9H-carbazole), 477 mg (3.9 mmol) of phenylboronic acid, 228 mg (0.168 mmol) of tetrakis(triphenylphosphine)palladium, 48 mL of tetrahydrofuran and 12 mL of water were successively added to a flask equipped with a magnetic stirrer, a condenser-water separator and a nitrogen inlet device. Under nitrogen, the mixture was heated to reflux at 70 °C for 12 hours. After the reaction was completed, 120 mL of dichloromethane was added, and the organic phase was obtained by extraction with 120 mL of water. After removing the solvent, 945 mg of white solid was obtained by silica gel column chromatography, and the yield was 58%.
[0050] (2) Synthesis of 9,9'-([1,1'-biphenyl]-3,5-diyl)bis(9H-carbazol-4-ol): 9,9'-([1,1'-biphenyl]-3,5-diyl)bis(9H-carbazol-4-methoxy) (5.0 g, 7.9 mmol) was added to anhydrous dichloromethane (50 mL) cooled in an ice bath under a nitrogen atmosphere. Then boron tribromide (10 g, 39.9 mmol) was slowly added to the mixture at 0 °C, and then the mixture was stirred at room temperature for 24 hours. The reaction was quenched by adding water, and the crude product was extracted with dichloromethane several times. The organic phase was dried over anhydrous magnesium sulfate. Finally, using silica gel as the stationary phase and a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 30:1 as the eluent, the mixture was separated by column chromatography to obtain 2.569 g of a white solid with a yield of 63%.
[0051] The 1H NMR data of the product are as follows: 1H NMR (500 MHz, Chloroform-d) δ 8.39 (d, J = 7.7 Hz, 2H), 7.93 (s, 2H), 7.79 (s, 1H), 7.71 (d, J = 7.4 Hz, 2H), 7.57 (d, J = 8.2 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.47–7.41 (m, 3H), 7.34 (t, J = 7.4 Hz, 2H), 7.31–7.26 (m, 2H), 7.17 (d, J = 8.2 Hz, 2H), 6.67 (d, J = 7.7 Hz, 2H), 5.44 (s, 2H).
[0052] (3) Synthesis of Compound 1: Sodium hydride (217 mg, 8 mmol) was added to a solution of 9,9'-([1,1'-biphenyl]-3,5-diyl)bis(9H-carbazol-4-ol) (1032 mg, 2 mmol) in 30 mL of N,N-dimethylformamide at room temperature. Under a nitrogen atmosphere, the reaction mixture was stirred for 3 hours and then cooled to 0 °C. 4-Vinylbenzyl chloride (614 mg, 8 mmol) was added dropwise. The reaction mixture was stirred at 60 °C for 24 hours and then quenched with water. The organic phase was extracted with dichloromethane several times and dried over anhydrous magnesium sulfate. Using a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 10:1 as the eluent, the mixture was separated by column chromatography to obtain 520.82 mg of Compound 1 as a white solid. Yield: 34.8%.
[0053] The 1H NMR data of the product are as follows: 1H NMR (500 MHz, Chloroform-d) δ 8.43 (d, J = 7.8 Hz, 2H), 7.93 (d, J = 1.6 Hz, 2H), 7.80 (s, 1H), 7.72 (d, J = 7.4 Hz, 2H), 7.60–7.55 (m, 6H), 7.50 (d, J = 8.1 Hz, 6H), 7.43 (t, J = 7.7 Hz, 3H), 7.36 (t, J = 8.1 Hz, 2H), 7.31 (t, J = 7.4 Hz, 2H), 7.22 (d, J = 8.2 Hz, 2H), 6.83 (d, J = 8.0 Hz, 2H), 6.79 (d, J = 10.9 Hz, 1H), 6.76 (d, J = 10.9 Hz, 1H), 5.81 (d, J = 17.6 Hz, 2H), 5.38 (s, 4H), 5.29 (d, J = 10.9 Hz, 2H).
[0054] The mass spectrum of the product: HR-MS (m / z): [M+1]+ calcd for [C54H40N2O2]+, 749.3160; found: 749.3154.
[0055] The reaction route for the synthesis of the above compound 1 is as follows:
[0056]
[0057] Example 2: Photophysical properties of the toluene solution of compound 1
[0058] Figure 1 The ultraviolet absorption spectrum, fluorescence spectrum and low-temperature phosphorescence spectrum of compound 1 are given. Compound 1 was formulated into a 7 mol / L toluene solution, and the solution was taken in a cuvette, and then the absorption spectrum and fluorescence spectrum were measured with a UV-visible spectrophotometer and a fluorescence photometer, respectively. The solution was taken in a quartz tube, cooled to -77 K, and then the low-temperature phosphorescence spectrum was measured with a phosphorescence photometer. The ultraviolet absorption peaks of compound 1 are located at 283 nm and 335 nm respectively, and the peak of the fluorescence spectrum of compound 1 is at 361 nm; and the triplet energy level of compound 1 can be calculated to be 2.98 eV through the low-temperature phosphorescence spectrum. The compound 1 prepared in this example has a relatively high triplet energy level, which can be beneficial to restricting excitons in the light-emitting layer, thereby improving the light-emitting efficiency.
[0059] Example 3: Solvent resistance test of compound 1
[0060] Figure 2The UV absorption spectra of Compound 1 and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) at a mass ratio of 9:1 after irradiation with 365-nm ultraviolet light for 3 minutes and before and after rinsing with chlorobenzene are presented. To test the solvent resistance of the crosslinked film of the compound, a chlorobenzene solution (5 mg / mL) of Compound 1 and PETMP was mixed at a mass ratio of 9:1 and spin-coated on a glass substrate. Complete crosslinking could be achieved by irradiating with 365-nm ultraviolet light for 3 minutes. Then, the crosslinked film was eluted with chlorobenzene three times, and the UV absorption spectra of the film before and after rinsing with chlorobenzene were measured. It was found that the absorbance of the film hardly changed before and after rinsing with chlorobenzene, indicating that the material was completely crosslinked at this temperature and exhibited good solvent resistance.
[0061] Example 4: Photo-crosslinked hole transport layer and its preparation in organic light-emitting devices
[0062] Place the conductive glass (ITO) substrate in a beaker, ultrasonically clean it with acetone and ethanol respectively, then take it out, dry it with nitrogen, and place it in an ultraviolet ozone generator for 20 minutes. After the treatment, spin-coat a layer of conductive polymer PEDOT:PSS on the ITO glass, and then bake it on a hot plate at 120 °C for 10 minutes. All subsequent operations are carried out in a glove box. Spin-coat a mixed chlorobenzene solution of Compound 1 (5 mg / mL) and thiol crosslinker PETMP (5 mg / mL) on the above PEDOT:PSS film, mix them at a mass ratio of 9:1, spin-coat at 1000 revolutions per minute on a spin coater, and then irradiate with ultraviolet light at 365 nm for 3 minutes to obtain a crosslinked hole transport layer. The light-emitting layer consists of 9-(3-(triphenylsilyl)phenyl)-9H-3,9′-bicarbazole (SiCzCz), polyvinylcarbazole (PVK), and 2,12-di-tert-butyl-5,9-bis(4-(tert-butyl)phenyl)-5,9-dihydro-5,9-diaza-13b-boroxino[3,2,1-de]anthracene (t-DABNA). Then, prepare a mixed solution of SiCzCz:PVK:t-DABNA according to a mass ratio of 77:20:3, spin-coat at 1000 revolutions per minute, and then heat it on a heating plate at 50 °C for 10 minutes. Subsequently, transfer the sample to a vacuum coating chamber, and sequentially evaporate a hole blocking layer of 2-phenyl-4,6-bis(3-(triphenylsilyl)phenyl)-1,3,5-triazine (mSiTrz, 10 nm), an electron transport layer of 1-(4-(10-([1,1'-biphenyl]-4-yl)anthracen-9-yl)phenyl)-2-ethyl-1H-benzo[d]imidazole (ANT-BIZ, 60 nm), an electron injection layer of lithium octahydroxyquinolate (Liq, 1 nm), and a cathode aluminum electrode (100 nm). After the device is prepared, the electroluminescence performance is tested in a glove box. As Figure 3As shown, the above device emits deep blue light with an emission peak at 458 nm and a full width at half maximum (FWHM) of 38 nm.
[0063] The specific embodiments of the present application have been described above. However, the protection scope of the present application is not limited thereto. Any person skilled in the art can easily conceive of changes or substitutions within the technical scope disclosed in the present application, and all such changes or substitutions should be covered within the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims
1. An olefin-functionalized carbazole derivative, characterized in that, The structural formula of the olefin-functionalized carbazole derivative is as follows: Among them, R1 is selected from any one of the following structures: R2 is selected from any one of vinyl, styryl, vinyl ether, acrylate group, methyl(vinyl) silanediamine, norbornene, maleimide, and methyl acrylate group.
2. The olefin-functionalized carbazole derivative according to claim 1, characterized in that, The structural formula of the olefin-functionalized carbazole derivative is any one of the following Formulas 1-28:
3. An organic electroluminescent material, characterized in that, Comprising the olefin-functionalized carbazole derivative according to any one of claims 1-2, the organic electroluminescent material specifically comprises a thin film structure, which is prepared by mixing the olefin-functionalized carbazole derivative with a thiol crosslinking agent and then through a photocrosslinking reaction.
4. The organic electroluminescent material according to claim 3, characterized in that, The thiol crosslinking agent is pentaerythritol tetra(3-mercaptopropionate), and the mass ratio of the olefin-functionalized carbazole derivative to the thiol crosslinking agent is (8-15):
1.
5. The organic electroluminescent material according to claim 3, wherein The ultraviolet light irradiation wavelength range of the photocrosslinking reaction is 250 nm to 400 nm, and the time of the photocrosslinking reaction is 30 seconds to 300 seconds.
6. The organic electroluminescent material according to claim 3, characterized in that, The organic electroluminescent material is used as a hole transport layer and / or a light-emitting layer of an electroluminescent device.
7. An organic electroluminescent device, characterized in that, Comprising a cathode layer, an anode layer, and an organic layer between the cathode layer and the anode layer, wherein the organic layer contains the olefin-functionalized carbazole derivative according to any one of claims 1-2 or its product.
8. The organic electroluminescent device according to claim 7, wherein, After the olefin-functionalized carbazole derivative and the thiol crosslinking agent are mixed, a thin film structure is formed through a photocrosslinking reaction for use in the organic electroluminescent device.
9. The organic electroluminescent device according to claim 8, characterized in that, The thiol crosslinking agent is pentaerythritol tetra(3-mercaptopropionate), the mass ratio of the olefin-functionalized carbazole derivative to the thiol crosslinking agent is (8-15):1, the ultraviolet light irradiation wavelength range of the photocrosslinking reaction is 250 nm to 400 nm, and the time of the photocrosslinking reaction is 30 seconds to 300 seconds.
10. Use of an olefin-functionalized carbazole derivative as described in any one of claims 1-2, characterized in that, The application is as a functional material in an organic electronic device, and the organic electronic device is selected from an organic electroluminescent device, an organic solar cell, an organic thin film transistor, a perovskite solar cell, or a perovskite light-emitting diode.