CN110305112B - Organic photoelectric material and application thereof - Google Patents

Organic photoelectric material and application thereof Download PDF

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CN110305112B
CN110305112B CN201810258588.9A CN201810258588A CN110305112B CN 110305112 B CN110305112 B CN 110305112B CN 201810258588 A CN201810258588 A CN 201810258588A CN 110305112 B CN110305112 B CN 110305112B
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穆广园
庄少卿
任春婷
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Wuhan Shangsai Optoelectronics Technology Co ltd
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Abstract

The invention belongs to the technical field of photoelectric material application technologies, and particularly relates to an organic photoelectric material and application thereof. The organic photoelectric material provided by the invention takes phenanthroimidazole and triazine as basic structural units to form a thermal-induced delayed fluorescent material, bonds or thickens triazine groups with stronger electron property and imidazole groups with phenanthroiene groups with larger conjugate planes, effectively improves the roll reduction of the device, simultaneously further modifies functional groups with stronger electron-withdrawing property to improve the exciton transmission and luminous performance of the device under high current density, and is an ideal light-emitting layer material, electron transmission material and light-emitting layer material in an organic electroluminescent device.

Description

Organic photoelectric material and application thereof
Technical Field
The invention belongs to the technical field of photoelectric material application technologies, and particularly relates to an organic photoelectric material and application thereof.
Background
Organic Light-Emitting diodes (OLEDs), also known as Organic electroluminescent displays and Organic Light-Emitting semiconductors, were discovered in 1979 by professor of chinese america dunng w.tang in the laboratory, and because of their advantages of self-luminescence, wide viewing angle, almost infinite contrast, low power consumption, very high response speed, and the like, they are widely used in the fields of mobile phones, digital cameras, notebook computers, vehicle-mounted displays, televisions, and lighting, the continuous development of OLED materials and the improvement of Organic Light-Emitting Diode performance have become the hot spots for research in the field of optoelectronics and technology.
OLED materials can be classified into three generations according to differences in light emission mechanism and discovery time. The first generation material was tris (8-hydroxyquinoline) aluminum (Alq) as a fluorescent material3) And anthracene, the theoretical limit of internal quantum efficiency of the fluorescent material under electroluminescent conditions is only 25%. The second generation material is represented by metal complexes such as iridium (Ir) and the like, and utilizes the high nuclear charge of heavy atoms to enhance the spin-orbit coupling effect in molecules, so that the singlet state and the triplet state wave functions are overlapped to a certain extent, the intersystem transition of S1-T1 and the radiation transition probability of T1-S0 are increased, and the internal quantum efficiency of 100% is realized. Most of the phosphorescent materials contain noble metals (such as iridium, platinum and the like), and the service life problem of the blue phosphorescent materials is difficult to solve, so that the application of the blue phosphorescent materials in the fields of display, illumination and the like is limited.
To overcome the disadvantages of these two types of materials, Adachi et al propose a third generation organic light emitting material, i.e., a thermally induced delayed fluorescent material, which emits light by forming singlet excitons through reverse intersystem crossing (RISC) from a triplet state to a singlet state. The materials generally have smaller singlet state-triplet state energy level difference, so that singlet state excitons and triplet state excitons formed under electric excitation can be fully utilized, and the internal quantum efficiency of the device can reach 100%. Meanwhile, the organic compound without heavy metal atoms is utilized to realize high efficiency equivalent to that of the phosphorescent material, so that the thermotropic delayed fluorescent material has wide application prospect in the field of photoelectric technology.
The quantum efficiency of the thermally induced delayed fluorescent material has greatly broken through the theoretical limit of the traditional fluorescent device, but actually faces the following three problems: (1) how to regulate the fine structure of designed molecule to make the difference between the spin coupling parameter and singlet-triplet energy level of the material and the radiation transition constant (k) under the singlet conditionf) The material can cooperate effectively, so that the material has high exciton utilization rate and high fluorescence radiation efficiency; (2) how to improve the radiation transition constant (k) of a material under a singlet state condition through material delocalization effect designf) Avoiding non-radiative transitions and making the radiative transition constant (k) of the singlet statef) Greater than the transition constant (k)isc) The efficiency roll-off of the device is improved from the viewpoint of regulating the exciton service life; (3) on the basis of the high-efficiency thermally induced delayed fluorescent material, how to match functional materials with different energy levels is realized from device junctionsThe angle improvement of the structure improves the performance of the device.
Disclosure of Invention
In order to solve the technical problems, the invention provides an organic photoelectric material, which is a compound formed by introducing functional groups by taking phenanthroimidazole and triazine as structural units, and the structural general formula of the organic photoelectric material is as follows:
Figure BDA0001609641720000021
wherein R is1、R2Is substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C5-C60Any one of the heteroaromatic groups of (a);
R3is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C5-C60Any one of the heteroaromatic group and substituted or unsubstituted amine group of (a);
R1、R2、R3the same or different.
Preferably, said R is1And R2Is any one of the following substituted or unsubstituted groups:
Figure BDA0001609641720000031
wherein x is a site attached to the triazine structure.
Preferably, the R1 and R2 are the same.
Preferably, R3Is any one of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl and substituted or unsubstituted diphenylamine, and R is3Are singly bound or directly condensed with the attached benzene rings.
The compounds 1-144 shown below are representative structures in keeping with the spirit and principles of the present invention, and it is to be understood that the specific structures of the following compounds are set forth only for the purpose of better illustrating the invention and are not to be construed as limiting the invention.
Figure BDA0001609641720000041
Figure BDA0001609641720000051
Figure BDA0001609641720000061
Figure BDA0001609641720000071
Figure BDA0001609641720000081
Figure BDA0001609641720000091
Figure BDA0001609641720000101
Figure BDA0001609641720000111
Figure BDA0001609641720000121
Figure BDA0001609641720000131
The invention also provides a preparation method of the organic photoelectric material, which comprises the following steps: the first step is as follows:
Figure BDA0001609641720000132
the second step is that:
Figure BDA0001609641720000133
wherein R is1、R2Is substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C5-C60Any one of the heteroaromatic groups of (a);
R3is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C5-C60Any one of the heteroaromatic group and substituted or unsubstituted amine group of (a);
R1、R2、R3the same or different.
Preferably, in the first step, the base is one of potassium carbonate, sodium carbonate or cesium carbonate, the solvent is one or more of toluene, xylene, N-dimethylacetamide, ethanol and water, and the catalyst is one of tetrakis (triphenylphosphine) palladium, palladium acetate and copper acetate.
Preferably, in the first step, 4, 6-dichloro-1, 3, 5-triazin-2-amine contains R1Substituted boronic acid derivatives, containing R2The boric acid derivative of the substituent, the catalyst and the alkali are mixed according to a molar ratio of 1:1: 1: 2-5 ‰:2-4, feeding the materials, wherein the solvent comprises toluene, ethanol and water, the volume ratio of the toluene to the ethanol to the water is 2:1:1, the reaction temperature is 60-100 ℃, and the reaction time is 4-36 hours.
Preferably, in the first step, 4, 6-dichloro-1, 3, 5-triazin-2-amine contains R1Substituted boronic acid derivatives, containing R2The boric acid derivative of the substituent, the catalyst and the alkali are mixed according to a molar ratio of 1:1: 1: 3 per mill: 2, the material is fed, the reaction temperature is 70-85 ℃, and the reaction time is 6-24 h.
Preferably, in said second step, R1、R2Correspondingly substituted 1,3, 5-triazin-2-amine derivatives, R3Corresponding substituted benzaldehyde derivatives,The phenanthrenequinone and the ammonium acetate are fed according to the molar ratio of 1:1-1.5:1-1.5:2-4, the reaction temperature is 80-120 ℃, and the reaction time is 4-12 h.
Preferably, in said second step, R1、R2Correspondingly substituted 1,3, 5-triazin-2-amine derivatives, R3Correspondingly substituted benzaldehyde derivatives, phenanthrenequinone and ammonium acetate are fed according to the molar ratio of 1:1.2:1.2:2, the reaction temperature is 90-115 ℃, and the reaction time is 5-10 h.
The invention also provides an application of the organic photoelectric material, and the organic photoelectric material is used for manufacturing an organic electroluminescent device, an organic solar cell or an organic field effect transistor.
The invention also provides an organic electroluminescent device which is formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, or formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode and a light emitting layer, wherein the light emitting layer, the electron transport layer and/or the light emitting layer at least comprise the organic photoelectric material.
The invention takes phenanthroimidazole and triazine as basic structural units to form the thermal-induced delayed fluorescent material. The triazine group and the imidazole group with stronger electron donating property are bonded or fused with the phenanthrene group with a larger conjugated plane to form a partially rigidized donor-acceptor type molecular structure, so that non-radiative transition caused by excited state vibration relaxation is weakened, the roll reduction of the device is effectively improved, meanwhile, the further modification of the functional group with stronger electron withdrawing property enhances the molecular distortion degree, an intramolecular charge transfer configuration is formed, the overlapping of HOMO-LUMO (the highest occupied molecular orbit and the lowest unoccupied molecular orbit) is effectively reduced, the singlet-triplet energy gap is further effectively reduced, the synergistic effect of high exciton utilization rate and high fluorescence radiation efficiency of the material is given, and the exciton transmission and light emitting performance of the device under high current density are improved. The organic electroluminescent device prepared by using the organic photoelectric material provided by the invention as a luminescent layer material, an electron transport material and a light-emitting layer material has high luminous brightness, high external quantum efficiency and low driving voltage, can effectively improve the roll-down and non-radiative transition of the device, emits pure deep blue light, and is an excellent OLED material.
Drawings
FIG. 1 is a device energy level diagram of compound 144;
FIG. 2 is a graph showing voltage-luminance characteristics of a device prepared by using compound 144 as a guest material of a light-emitting layer and not containing the compound of the present invention;
FIG. 3 is a graph of voltage-luminance characteristics of compound 144 as a guest material in a light emitting layer and a device prepared without the compound of the present invention;
fig. 4 is a graph of current efficiency versus current density characteristics for compound 144 as a guest material for a light emitting layer and for a device prepared without the compound of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. Any simple modifications, equivalent changes and the like to the following embodiments according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention. The present invention is not limited to the contents described in the following embodiments.
Example 1
The compound 3 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000151
(1) Into a 500mL three-necked flask were charged 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.50g, 100mmol), 4-tert-butylboronic acid (35.60g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL, under N2Tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) was added under protection, the reaction was controlled at 85 ℃ for 12h, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice, adding active carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing twice with ethanol, and vacuum drying to obtain 32.44g of 4, 6-bis (4-tert-butylphenyl) -1,3, 5-triazine-2-amine with yield of 90%.
(2) In a 500ml three-mouth bottle,phenanthrenequinone (10.41g, 50mmol), 4, 6-bis (4-tert-butylphenyl) -1,3, 5-triazin-2-amine (21.63g, 60mmol), 4-methylbenzaldehyde (9.73g, 60mmol), and ammonium acetate (7.71g, 100mmol) were dissolved in 250mL of glacial acetic acid, and the mixture was charged into a reactor, heated to 115 ℃ under a nitrogen atmosphere, reacted for 8 hours, and the completion of the reaction was monitored by a liquid phase. Cooling to room temperature, washing twice with water, adding activated carbon for decolorization, filtering, concentrating, recrystallizing twice with ethyl acetate, and drying under vacuum to obtain the target compound 30.18g with yield of 87%. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 693.9395, theoretical molecular weight 693.9390; call for C48H47N5(％):C 83.08,H 6.83,N10.09Found:C 83.10,H 6.84,N 10.06。
Example 2
The compound 12 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000161
(1) In a 500mL three-necked flask, 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.50g, 100mmol), (9, 9-dimethyl-9H-fluoren-2-yl) boronic acid (47.62g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL, in N2Tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) was added under protection, the reaction was controlled at 85 ℃ for 12h, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice, adding active carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing twice with ethanol, and vacuum drying to obtain 42.29g of 4, 6-bis (9, 9-methyl-9H-fluoren-2-yl) -1,3, 5-triazine-2-amine with yield of 88%.
(2) In a 500mL three-necked flask, phenanthrenequinone (10.41g, 50mmol), 4, 6-bis (9, 9-methyl-9H-fluoren-2-yl) -1,3, 5-triazine-2-amine (28.84g, 60mmol), benzaldehyde (6.37g, 60mmol) and ammonium acetate (7.71g, 100mmol) are dissolved in 250mL of glacial acetic acid, added to a reactor, heated to 115 ℃ under nitrogen atmosphere for reaction for 8H, and the reaction completion is monitored by a liquid phase. Cooling to room temperature, washing with water twice, decolorizing with active carbon, filtering, concentrating, recrystallizing with ethyl acetate twice, and vacuum drying to obtain the final productThe title compound (32.21 g) was obtained in 85% yield. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 757.9417, theoretical molecular weight 757.9410; call for C54H39N5(％):C 85.57,H 5.19,N 9.24Found:C 85.54,H 5.20,N 9.26。
Example 3
The compound 21 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000171
(1) In a 500mL three-necked flask, 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.50g, 100mmol), phenylboronic acid (24.39g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL were added under N2Tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) was added under protection, the reaction was controlled at 85 ℃ for 12h, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice, adding active carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing the product twice with ethanol, and drying under vacuum to obtain 22.35g of 4, 6-diphenyl-1, 3, 5-triazine-2-amine with yield of 90%.
(2) In a 500ml three-necked flask, phenanthrenequinone (10.41g, 50mmol), 4, 6-diphenyl-1, 3, 5-triazin-2-amine (14.89g, 60mmol) and [1,1' -biphenyl were added]4-formaldehyde (10.93g, 60mmol) and ammonium acetate (7.71g, 100mmol) are dissolved in 250mL of glacial acetic acid, added to a reactor, heated to 115 ℃ under nitrogen atmosphere, reacted for 8h, and the completion of the reaction is monitored by a liquid phase. Cooling to room temperature, washing twice with water, adding activated carbon for decolorization, filtering, concentrating, recrystallizing twice with ethyl acetate, and drying under vacuum to obtain the target compound 26.17g with yield 87%. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 601.7135, theoretical molecular weight 601.7130; call for C42H27N5(％):C 83.84,H 4.52,N11.64Found:C 83.85,H 4.55,N 11.60。
Example 4
The compound 40 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000181
(1) In a 500mL three-necked flask, 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.50g, 100mmol), (dibenzofuran-2-yl) boronic acid (42.40g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL were added under N2Tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) was added under protection, the reaction was controlled at 85 ℃ for 12h, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice, adding active carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing twice with ethanol, and vacuum drying to obtain 37.27g of 4, 6-bis (dibenzofuran-2-yl) -1,3, 5-triazine-2-amine with yield of 87%.
(2) In a 500ml three-necked flask, phenanthrenequinone (10.41g, 50mmol), 4, 6-bis (dibenzofuran-2-yl) -1,3, 5-triazin-2-amine (25.71g, 60mmol) and [1,1' -biphenyl were added]-3-formaldehyde (10.93g, 60mmol) and ammonium acetate (7.71g, 100mmol) are dissolved in 250mL glacial acetic acid and added to a reactor, and the temperature is raised to 115 ℃ for reaction for 8h under nitrogen atmosphere, and the completion of the reaction is monitored by a liquid phase. Cooling to room temperature, washing twice with water, adding active carbon for decolorization, filtering, concentrating, recrystallizing twice with ethyl acetate, and drying under vacuum to obtain 33.23g of target compound with 85% yield. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 781.8748, theoretical molecular weight 781.8750; call for C54H31N5O2(％):C82.95,H 4.00,N 8.96Found:C 82.91,H 4.06,N 8.94。
Example 5
The compound 58 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000191
(1) Into a 500mL three-necked flask were charged 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.50g, 100mmol), (naphthalen-2-yl) boronic acid (34.40g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL, under N2Adding tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) under protection, controlling the reaction at 85 ℃, and reacting for 12hThe liquid phase monitors the completion of the reaction. Cooling to room temperature, washing twice, adding active carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing twice with ethanol, and vacuum drying to obtain 30.66g of 4, 6-di (naphthalene-2-yl) -1,3, 5-triazine-2-amine with yield of 88%.
(2) In a 500mL three-necked flask, phenanthrenequinone (10.41g, 50mmol), 4, 6-bis (naphthalen-2-yl) -1,3, 5-triazin-2-amine (20.90g, 60mmol), 2-naphthaldehyde (9.37g, 60mmol) and ammonium acetate (7.71g, 100mmol) are dissolved in 250mL glacial acetic acid, added to a reactor, heated to 115 ℃ under nitrogen atmosphere for reaction for 8h, and the completion of the reaction is monitored by a liquid phase. Cooling to room temperature, washing twice with water, adding active carbon for decolorization, filtering, concentrating, recrystallizing twice with ethyl acetate, and drying under vacuum to obtain 28.04g of target compound with yield of 83%. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 675.7955, theoretical molecular weight 675.7950; call for C48H29N5(％):C 85.31,H 4.33,N10.36Found:C 85.33,H 4.34,N 10.33。
Example 6
The compound 68 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000192
(1) Into a 500mL three-necked flask were charged 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.50g, 100mmol), (dibenzothiophen-1-yl) boronic acid (45.61g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL, and the mixture was stirred in N2Tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) was added under protection, the reaction was controlled at 85 ℃ for 12h, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice, adding activated carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing twice with ethanol, and vacuum drying to obtain 40.07g of 4, 6-di (dibenzothiophene-1-yl) -1,3, 5-triazine-2-amine with yield of 87%.
(2) To a 500ml three-necked flask, phenanthrenequinone (10.41g, 50mmol), 4, 6-bis (dibenzothiophen-1-yl) -1,3, 5-triazin-2-amine (27.63g, 60mmol), 2-naphthaldehyde (9.37g, 60mmol), ammonium acetate (7.71g,100mmol) of the reaction solution is dissolved in 250mL of glacial acetic acid and added into a reactor, the temperature is raised to 115 ℃ for reaction for 8 hours under the nitrogen atmosphere, and the completion of the reaction is monitored by a liquid phase. Cooling to room temperature, washing twice with water, adding activated carbon for decolorization, filtering, concentrating, recrystallizing twice with ethyl acetate, and drying under vacuum to obtain 33.31g of target compound with yield of 82%. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 787.9587, theoretical molecular weight 787.9590; call for C52H29N5S2(％):C 79.26,H 3.71,N8.89Found:C 79.25,H 3.76,N 8.85。
Example 7
The compound 86 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000201
(1) In a 500mL three-necked flask, 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.50g, 100mmol), phenylboronic acid (24.39g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL were added under N2Tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) was added under protection, the reaction was controlled at 85 ℃ for 12h, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice, adding active carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing the product twice with ethanol, and drying under vacuum to obtain 22.35g of 4, 6-diphenyl-1, 3, 5-triazine-2-amine with yield of 90%.
(2) In a 500mL three-necked bottle, phenanthrenequinone (10.41g, 50mmol), 4, 6-diphenyl-1, 3, 5-triazine-2-amine (14.89g, 60mmol), 4-diphenylaminobenzaldehyde (16.40g, 60mmol) and ammonium acetate (7.71g, 100mmol) are added to a reactor dissolved in 250mL of glacial acetic acid, the temperature is raised to 115 ℃ under nitrogen atmosphere, the reaction is carried out for 8h, and the completion of the reaction is monitored by a liquid phase. Cooling to room temperature, washing twice with water, adding activated carbon for decolorization, filtering, concentrating, recrystallizing twice with ethyl acetate, and drying under vacuum to obtain 29.79g of target compound with 86% yield. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 692.8264, theoretical molecular weight 692.8260; call for C48H32N6(％):C 83.21,H 4.66,N12.13Found:C 83.23,H 4.64,N 12.13。
Example 8
The compound 114 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000211
(1) In a 500mL three-necked flask, 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.50g, 100mmol), phenylboronic acid (24.39g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL were added under N2Tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) was added under protection, the reaction was controlled at 85 ℃ for 12h, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice, adding active carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing the product twice with ethanol, and drying under vacuum to obtain 22.35g of 4, 6-diphenyl-1, 3, 5-triazine-2-amine with yield of 90%.
(2) In a 500mL three-necked bottle, phenanthrenequinone (10.41g, 50mmol), 4, 6-diphenyl-1, 3, 5-triazine-2-amine (14.89g, 60mmol), 9- (3-formylphenyl) -9H-carbazole (16.22g, 60mmol) and ammonium acetate (7.71g, 100mmol) are added to a reactor dissolved in 250mL of glacial acetic acid, the temperature is raised to 115 ℃ under the nitrogen atmosphere for reaction for 8H, and the completion of the reaction is monitored by a liquid phase. Cooling to room temperature, washing twice with water, adding active carbon for decolorization, filtering, concentrating, recrystallizing twice with ethyl acetate, and drying under vacuum to obtain 29.70g of target compound with yield of 86%. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 690.8104, theoretical molecular weight 690.8100; call for C48H30N6(％):C 83.46,H 4.38,N12.17Found:C 83.43,H 4.41,N 12.16。
Example 9
The compound 127 provided by the present invention can be synthesized by the following method.
Figure BDA0001609641720000221
(1) In a 500ml three-necked flask, 4, 6-dichloro-1, 3, 5-triazin-2-amine (16.5) was added0g, 100mmol) of [1,1' -phenyl group]-3-ylboronic acid (39.60g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethanol 75mL, water 75mL in N2Tetrakis (triphenylphosphine) palladium (0.35g, 3mmol) was added under protection, the reaction was controlled at 85 ℃ for 12h, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice, adding active carbon for decolorization, filtering, concentrating to obtain light yellow solid, recrystallizing with ethanol twice, and vacuum drying to obtain 4, 6-bis ([1,1' -biphenyl)]35.24g of (E) -3-yl) -1,3, 5-triazin-2-amine, yield 88%.
(2) In a 500ml three-necked flask, phenanthrenequinone (10.41g, 50mmol) and 4, 6-bis ([1,1' -biphenyl) were added]-3-yl) -1,3, 5-triazin-2-amine (24.03g, 60mmol), 4- (naphthalen-2-yl) benzaldehyde (13.94g, 60mmol), ammonium acetate (7.71g, 100mmol) were dissolved in 250mL of glacial acetic acid and added to the reactor, and the temperature was raised to 115 ℃ for 8h under nitrogen atmosphere, and the completion of the reaction was monitored by liquid phase. Cooling to room temperature, washing twice with water, adding active carbon for decolorization, filtering, concentrating, recrystallizing twice with ethyl acetate, and drying under vacuum to obtain 33.77g of target compound with yield of 84%. The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 803.9695, theoretical molecular weight 803.9690; call for C58H37N5(％):C86.65,H 4.64,N 8.71Found:C 86.67,H 4.65,N 8.68。
Example 10
In this example, the compound was used as guest material of light-emitting layer in organic electroluminescent device to prepare a plurality of organic electroluminescent devices having a structure of substrate/anode/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/organic light-Emitting Layer (EL)/Electron Transport Layer (ETL)/electron injection layer (EI)/cathode,
the substrate is a glass substrate, the anode is Indium Tin Oxide (ITO), and the hole injection layer is molybdenum trioxide (MoO)3) The hole transport layer is 4,4' -tri (carbazole-9-yl) triphenylamine (TCTA), and the main material of the organic luminescent layer is bis [2- ((oxo) diphenylphosphino) phenyl]The guest material of the organic light-emitting layer is the compound 3, the compound 12, the compound 21, the compound 40, the compound 58, the compound 68, the compound 86, the compound 114 and the compound 127 provided by the invention, and the electron transport layer is the compound 3,3'- [5' - [3- (S-P-O-3-pyridyl) phenyl][1,1':3', 1' -terphenyl]-3,3 "-diyl]Bipyridine (TmPyPb), the electron injection layer was lithium fluoride (LiF), and the cathode was aluminum (Al).
The ITO glass is sequentially cleaned in a cleaning agent and deionized water by ultrasonic waves for 30 minutes, then dried in vacuum for 2 hours (105 ℃), then put into a plasma reactor for oxygen plasma treatment for 5 minutes, transferred into a vacuum chamber to prepare an organic film and a metal electrode, and then a layer of 10nm MoO is prepared by a vacuum evaporation method3Then 60nm of TCTA is evaporated, then on the basis of this a 12nm layer of DPEPO containing 5% (by mass) of the compound according to the invention is evaporated in vacuo, and finally a layer of TmPyPb at 15nm, LiF at 1nm and Al at 100nm is evaporated.
The organic electroluminescent device properties are given in the following table:
Figure BDA0001609641720000231
as can be seen from the above table and FIG. 1, the further modification of the functional group with strong electron-withdrawing property strengthens the distortion degree of the molecular configuration of phenanthroimidazotriazines, and intramolecular charge transfer effectively reduces the overlapping of the compound HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital), thereby effectively reducing the singlet-triplet energy gap, so that the glass substrate/ITO/MoO3TCTA/DPEPO: the energy level matching degree between materials of functional layers of the device prepared by taking the 5 wt% compound 144/TmPyPb/LiF/Al as the structure is better, and the energy transfer and recombination excitation efficiency between host materials and guest materials of a light-emitting layer is higher.
As can be seen from the above table and fig. 2 to 4, compared with a device prepared without the organic photoelectric material provided by the present invention, the device prepared by using the organic photoelectric material provided by the present invention as the guest material of the light-emitting layer has significant improvements in terms of starting voltage, light-emitting brightness, current efficiency, lumen efficiency and external quantum efficiency, and the non-radiative transition and roll-down problems of the device are effectively improved.
Example 11
In this example, the compound was used as a host material of a light emitting layer in an organic electroluminescent device to prepare a plurality of organic electroluminescent devices having a structure of substrate/anode/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/electron injection layer (EI)/cathode,
the substrate is a glass substrate, the anode is Indium Tin Oxide (ITO), and the hole injection layer is molybdenum trioxide (MoO)3) The hole transport layer is 4,4' -tri (carbazole-9-yl) triphenylamine (TCTA), the organic luminescent layer host material is the compound 3, the compound 21, the compound 86 and the compound 127 provided by the invention, and the organic luminescent layer guest material is bis (4, 6-difluorophenylpyridine-N, C)2) The pyridine formyl iridium (Firpic) and the electron transport layer is 3,3'- [5' - [3- (3-pyridyl) phenyl][1,1':3', 1' -terphenyl]-3,3 "-diyl]Bipyridine (TmPyPb), the electron injection layer was lithium fluoride (LiF), and the cathode was aluminum (Al).
The ITO glass is sequentially cleaned in a cleaning agent and deionized water by ultrasonic waves for 30 minutes, then dried in vacuum for 2 hours (105 ℃), then put into a plasma reactor for oxygen plasma treatment for 5 minutes, transferred into a vacuum chamber to prepare an organic film and a metal electrode, and then a layer of 10nm MoO is prepared by a vacuum evaporation method3Then 60nm TCTA is evaporated, then on the basis of this, a 12nm compound provided by the invention containing 5% (by mass fraction) Firpic is evaporated in vacuum, and finally a layer of 15nm TmPyPb, 1nm LiF and 100nm Al is evaporated.
The organic electroluminescent device properties are given in the following table:
Figure BDA0001609641720000241
as can be seen from the above table, compared with a device prepared without the organic photoelectric material provided by the present invention, the organic photoelectric material provided by the present invention is an ideal light emitting layer host material, and the dense donor-acceptor group combination provides a path for injecting both electrons and holes, so that the performance of the device in terms of starting voltage, current efficiency, lumen efficiency and external quantum efficiency is significantly improved, and the non-radiative transition and roll-down problems of the device are effectively improved.
Example 12
In this example, the compound was used as an electron transport material in an organic electroluminescent device to prepare a plurality of organic electroluminescent devices having a structure of substrate/anode/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/electron injection layer (EI)/cathode,
the substrate is a glass substrate, the anode is Indium Tin Oxide (ITO), and the hole injection layer is molybdenum trioxide (MoO)3) The hole transport layer is 4,4' -tri (carbazole-9-yl) triphenylamine (TCTA), and the main material of the organic luminescent layer is bis [2- ((oxo) diphenylphosphino) phenyl]Ether (DPEPO), and the guest material of the organic luminescent layer is bis (4, 6-difluorophenylpyridine-N, C)2) The electron transport layer is compound 3, compound 21, compound 40 and compound 58 provided by the invention, the electron injection layer is lithium fluoride (LiF), and the cathode is aluminum (Al).
The ITO glass is sequentially cleaned in a cleaning agent and deionized water by ultrasonic waves for 30 minutes, then dried in vacuum for 2 hours (105 ℃), then put into a plasma reactor for oxygen plasma treatment for 5 minutes, transferred into a vacuum chamber to prepare an organic film and a metal electrode, and then a layer of 10nm MoO is prepared by a vacuum evaporation method3Then 60nm of TCTA is evaporated, then on the basis of this, a 12nm layer of DPEPO containing 5% (by mass) Firpic is evaporated in a vacuum, and finally a 15nm layer of the compound provided by the invention, 1nm of LiF and 100nm of Al is evaporated.
The organic electroluminescent device properties are given in the following table:
Figure BDA0001609641720000251
as can be seen from the above table, compared with a device prepared without the organic photoelectric material provided by the present invention, the organic photoelectric material provided by the present invention is an ideal electron transport material, the electron transport rate and the hole transport rate are effectively balanced, the problem of exciton non-recombination consumption is improved, and the performance of the device in the aspects of starting voltage, current efficiency and lumen efficiency is significantly improved.
Example 13
In this example, the compound was used as a light emitting layer in an organic electroluminescent device to prepare a plurality of organic electroluminescent devices having a structure of substrate/anode/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/electron injection layer (EI)/cathode/light emitting layer,
the substrate is a glass substrate, the anode is Indium Tin Oxide (ITO), and the hole injection layer is molybdenum trioxide (MoO)3) The hole transport layer is 4,4' -tri (carbazole-9-yl) triphenylamine (TCTA), and the main material of the organic luminescent layer is bis [2- ((oxo) diphenylphosphino) phenyl]Ether (DPEPO), and the guest material of the organic luminescent layer is bis (4, 6-difluorophenylpyridine-N, C)2) The pyridine formyl iridium (Firpic) and the electron transport layer is 3,3'- [5' - [3- (3-pyridyl) phenyl][1,1':3', 1' -terphenyl]-3,3 "-diyl]Bipyridine (TmPyPb), the electron injection layer is lithium fluoride (LiF), the cathode is aluminum (Al), and the light emitting layer is the compound 3, the compound 21, the compound 58 and the compound 114 provided by the invention.
The ITO glass is sequentially cleaned in a cleaning agent and deionized water by ultrasonic waves for 30 minutes, then dried in vacuum for 2 hours (105 ℃), then put into a plasma reactor for oxygen plasma treatment for 5 minutes, transferred into a vacuum chamber to prepare an organic film and a metal electrode, and then a layer of 10nm MoO is prepared by a vacuum evaporation method3Then 60nm TCTA is evaporated, then on the basis of this, a 12nm DPEPO layer containing 5% (by mass fraction) Firpic is evaporated in vacuum, and finally a 15nm TmPyPb layer, 1nm LiF, 100nm Al and 15nm of the compound provided by the present invention are evaporated.
The organic electroluminescent device properties are given in the following table:
Figure BDA0001609641720000261
as can be seen from the above table, compared with a device prepared without the organic photoelectric material provided by the present invention, the organic photoelectric material provided by the present invention is an ideal light-emitting layer material, which reduces the loss of light between interfaces, effectively improves the light extraction efficiency of the device, and significantly improves the performance of the device in the aspects of lumen efficiency and external quantum efficiency.
Example 14
In this example, the organic electroluminescent device was prepared without the compound provided by the present invention, and had a structure of substrate/anode/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/electron injection layer (EI)/cathode, glass substrate as substrate, Indium Tin Oxide (ITO) as anode, molybdenum trioxide (MoO) as hole injection layer (EI)/cathode3) The hole transport layer is 4,4' -tri (carbazole-9-yl) triphenylamine (TCTA), and the main material of the organic luminescent layer is bis [2- ((oxo) diphenylphosphino) phenyl]Ether (DPEPO), and the guest material of the organic luminescent layer is bis (4, 6-difluorophenylpyridine-N, C)2) The pyridine formyl iridium (Firpic) and the electron transport layer is 3,3'- [5' - [3- (3-pyridyl) phenyl][1,1':3', 1' -terphenyl]-3,3 "-diyl]Bipyridine (TmPyPb), the electron injection layer was lithium fluoride (LiF), and the cathode was aluminum (Al).
The ITO glass is sequentially cleaned in a cleaning agent and deionized water by ultrasonic waves for 30 minutes, then dried in vacuum for 2 hours (105 ℃), then put into a plasma reactor for oxygen plasma treatment for 5 minutes, transferred into a vacuum chamber to prepare an organic film and a metal electrode, and then a layer of 10nm MoO is prepared by a vacuum evaporation method3Then 60nm of TCTA is evaporated, then on the basis of this a 12nm layer of DPEPO containing 5% (by mass fraction) Firpic is evaporated in a vacuum, and finally a layer of TmPyPb at 15nm, LiF at 1nm and Al at 100nm is evaporated.
The organic electroluminescent device properties are given in the following table:
Figure BDA0001609641720000271
although the present invention has been described in connection with the embodiments, the present invention is not limited to the embodiments, and it should be understood that any modifications, equivalents, improvements, etc. made in the spirit of the present invention are included in the scope of the present invention.

Claims (8)

1. The organic photoelectric material is characterized in that the material is a compound formed by introducing functional groups by taking phenanthroimidazole and triazine as structural units, and the structural general formula of the compound is as follows:
Figure FDA0002600403310000011
the R is1And R2Is any one of the following groups:
Figure FDA0002600403310000012
wherein is a site attached to the triazine structure;
r3 is phenyl or naphthyl, wherein when R3 is phenyl, R3 is connected with a connected benzene ring through a single bond or directly condensed, and when R3 is naphthyl, R3 is connected with a connected benzene ring through a single bond;
R1、R2、R3the same or different.
2. The organic photoelectric material according to claim 1, wherein R is1And R2The same is true.
3. A method for preparing an organic photoelectric material according to claim 1 or 2, comprising the following route:
the first step is as follows:
Figure FDA0002600403310000021
the second step is that:
Figure FDA0002600403310000022
the R is1And R2Is any one of the following groups:
Figure FDA0002600403310000023
wherein is a site attached to the triazine structure;
r3 is phenyl or naphthyl, wherein when R3 is phenyl, R3 is connected with a connected benzene ring through a single bond or directly condensed, and when R3 is naphthyl, R3 is connected with a connected benzene ring through a single bond;
R1、R2、R3the same or different.
4. The method according to claim 3, wherein the base in the first step is one of potassium carbonate, sodium carbonate or cesium carbonate, the solvent is one or more of toluene, xylene, N-dimethylacetamide, ethanol and water, and the catalyst is one of tetrakis (triphenylphosphine) palladium, palladium acetate and copper acetate.
5. The process according to claim 4, wherein in the first step, 4, 6-dichloro-1, 3, 5-triazin-2-amine having R is used1Substituted boronic acid derivatives, containing R2The boric acid derivative of the substituent, the catalyst and the alkali are mixed according to a molar ratio of 1:1: 1: 2-5 ‰:2-4, feeding; the solvent is toluene, ethanol and water, and the volume ratio of the toluene to the ethanol to the water is 2:1: 1; the reaction temperature is controlled between 60 ℃ and 100 ℃, and the reaction time is 4 to 36 hours.
6. The process according to claim 3, wherein in the second step, R is1、R2Correspondingly substituted 1,3, 5-triazin-2-amine derivatives, R3Feeding the corresponding substituted benzaldehyde derivative, the phenanthrenequinone and the ammonium acetate according to a molar ratio of 1:1-1.5:1-1.5: 2-4; the reaction temperature is controlled to be 80-120 ℃; the reaction time is 4-12 h.
7. Use of the organic photovoltaic material according to claim 1 or 2 for the manufacture of an organic electroluminescent device, an organic solar cell or an organic field effect transistor.
8. An organic electroluminescent device, which is formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, or formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode and a light emitting layer, wherein the light emitting layer, the electron transport layer and/or the light emitting layer at least comprise the organic photoelectric material according to claim 1 or 2.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140145149A1 (en) * 2012-11-26 2014-05-29 Universal Display Corporation Organic Luminescent Compound With Delayed Fluorescence
US9893300B1 (en) * 2017-03-08 2018-02-13 National Tsing Hua University Phenanthroimidazole compound and organic light-emitting diode including the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
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US20140145149A1 (en) * 2012-11-26 2014-05-29 Universal Display Corporation Organic Luminescent Compound With Delayed Fluorescence
US9893300B1 (en) * 2017-03-08 2018-02-13 National Tsing Hua University Phenanthroimidazole compound and organic light-emitting diode including the same

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