CN110305112A - A kind of organic photoelectrical material and its application - Google Patents

A kind of organic photoelectrical material and its application Download PDF

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CN110305112A
CN110305112A CN201810258588.9A CN201810258588A CN110305112A CN 110305112 A CN110305112 A CN 110305112A CN 201810258588 A CN201810258588 A CN 201810258588A CN 110305112 A CN110305112 A CN 110305112A
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CN110305112B (en
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穆广园
庄少卿
任春婷
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WUHAN SHANGSAI PHOTOELECTRIC TECHNOLOGY Co Ltd
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WUHAN SHANGSAI PHOTOELECTRIC TECHNOLOGY Co Ltd
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Abstract

The invention belongs to photoelectric material applicating technology technical fields, and in particular to a kind of organic photoelectrical material and its application.Organic photoelectrical material provided by the present invention is using phenanthro- imidazoles and triazine as basic structural unit, form a kind of thermotropic delayed fluorescence material, the stronger triazine group of electron, imidazole group with larger conjugate planes phenanthryl group key even or it is thick and effectively improve device drop roll, simultaneously, the further modification of electron-withdrawing stronger functional groups improves the exciton transfer and luminescent properties of device device under high current density, is a kind of ideal emitting layer material, electron transport material and photosphere material out in organic electroluminescence device.

Description

A kind of organic photoelectrical material and its application
Technical field
The invention belongs to photoelectric material applicating technology technical field, in particular to a kind of organic photoelectrical material and its application.
Background technique
It is aobvious that Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED) is also known as organic electric laser Show, organic luminous semiconductor, Deng Qingyun (Ching W.Tang) taught by Chinese descendant in America and was found in the lab in 1979, Since it has many advantages, such as self-luminous, wide viewing angle, almost infinite high contrast, extensive compared with low power consumption, high reaction speed Apply to the fields such as mobile phone, DV, laptop, car-mounted display, TV and illumination, OLED material does not turn off The promotion of hair and Organic Light Emitting Diode performance becomes the hot spot of Optoelectronics Technology area research.
Difference of the OLED material according to luminescence mechanism and discovery time, can be divided into three generations.First generation material is with phosphor Expect three (8-hydroxyquinoline) aluminium (Alq3) and anthracene class aromatic compound be representative, under the conditions of electroluminescent, fluorescent material it is interior Quantum efficiency theoretical limit is only 25%.Second generation material utilizes the height of heavy atom using metal complexs such as iridium (Ir) as representative Nuclear charge acts on to enhance the SO coupling of intramolecular, occurs that singlet state to a certain extent with triplet wave function Overlapping, increases the intersystem transition of S1-T1 and the radiative transistion probability of T1-S0, to realize 100% internal quantum efficiency.This Class phosphor material contains precious metal (such as iridium, platinum) mostly, and the life problems of blue emitting phosphor material are difficult to solve, and constrain Its application in the fields such as display and illumination.
The shortcomings that in order to overcome these two types of materials, Adachi etc., which is proposed, to be jumped using triplet between the inverse system of singlet state It moves (reverse intersystem-crossing, RISC) and forms singlet excitons and luminous third generation organic light emission material Material --- thermotropic delayed fluorescence material.Such material generally has lesser singlet-triplet poor, this can be sufficiently sharp With the singlet exciton and triplet excitons for being electrically excited lower formation, the internal quantum efficiency of device can achieve 100%.Meanwhile benefit With without containing heavy metal atom organic compound realize with the comparable high efficiency of phosphor material so that thermotropic delayed fluorescence material In Optoelectronics Technology field, application prospect is very wide.
The quantum efficiency of thermotropic delayed fluorescence material has breached the theoretical limit of conventional fluorescent device significantly, but practical On the problem of facing in terms of following three: (1) how to regulate and control the fine structure of designed molecule, make the spin coupling parameter of material With the radiation transistion constant (k under the conditions of singlet-triplet is poor and singlet statef) can effectively cooperate with, so that Material has both high exciton utilization rate and high fluorescent radiation efficiency；(2) how to be designed by material delocalization effect and improve material in list Radiation transistion constant (k under the conditions of weight statef), nonradiative transition is avoided, the radiation transistion constant (k of singlet state is madef) it is greater than transition Constant (kisc), improve device efficiency from regulation exciton lifetime angle and roll-offs；(3) on the basis of efficient thermotropic delayed fluorescence material On, the functional material of different energy levels how is matched, improves from the angle of device architecture and promotes device performance.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of organic photoelectrical material, the material is with phenanthro- imidazoles The compound that functional groups are constituted is introduced for structural unit with triazine, general structure such as following structural:
Wherein, R1、R2For substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C5-C60Heteroaryl perfume base In any one；
R3For hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C5-C60Heteroaryl perfume base, any one in substituted or unsubstituted amido；
R1、R2、R3It is identical or different.
Preferably, the R1And R2It is any one in substituted or unsubstituted following groups:
Wherein, * is the site connecting with triazine structure.
Preferably, the R1 and R2 is identical.
Preferably, R3For hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted It is phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted carbazyl, any one in substituted or unsubstituted hexichol amido Kind, the R3Singly-bound is connected or directly condenses between the phenyl ring of connection.
Compound 1-144 shown in following formula is the representative structure for meeting spirit of that invention and principle, it should be understood that is listed following The specific structure of compound is intended merely to preferably explain the present invention, is not limitation of the present invention.
The present invention also provides a kind of preparation methods of above-mentioned organic photoelectrical material, including following route: step 1:
Step 2:
Wherein, R1、R2For substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C5-C60Heteroaryl perfume base In any one；
R3For hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C5-C60Heteroaryl perfume base, any one in substituted or unsubstituted amido；
R1、R2、R3It is identical or different.
Preferably, in the first step, the alkali is one of potassium carbonate, sodium carbonate or cesium carbonate, and the solvent is One of toluene, dimethylbenzene, n,N-dimethylacetamide, ethyl alcohol, water are a variety of, and the catalyst is four (triphenylphosphines) One of palladium, palladium acetate, copper acetate.
Preferably, in the first step, 4,6- bis- chloro-1,3,5-triazines -2- amine contain R1The boronic acid derivatives of substituent group, Containing R2Boronic acid derivatives, catalyst, the alkali of substituent group feed intake according to molar ratio 1:1:1:2 ‰ -5 ‰: 2-4, and the solvent includes Toluene, second alcohol and water, and the volume ratio of toluene, ethyl alcohol, water is 2:1:1, reaction temperature is 60 DEG C -100 DEG C, reaction time 4- 36 hours.
Preferably, in the first step, 4,6- bis- chloro-1,3,5-triazines -2- amine contain R1The boronic acid derivatives of substituent group, Containing R2Boronic acid derivatives, catalyst, the alkali of substituent group feed intake according to molar ratio 1:1:1:3 ‰: 2, and reaction temperature is 70 DEG C -85 DEG C, reaction time 6-24h.
Preferably, in the second step, R1、R2The corresponding 1,3,5- triazine -2- amine derivative replaced, R3Corresponding substitution Benzaldehyde derivative, phenanthrenequione, ammonium acetate feed intake according to molar ratio 1:1-1.5:1-1.5:2-4, and reaction temperature is 80-120 DEG C, instead It is 4-12h between seasonable.
Preferably, in the second step, R1、R2The corresponding 1,3,5- triazine -2- amine derivative replaced, R3Corresponding substitution Benzaldehyde derivative, phenanthrenequione, ammonium acetate feed intake according to molar ratio 1:1.2:1.2:2, and reaction temperature is 90-115 DEG C, the reaction time For 5-10h.
The present invention also provides a kind of application of above-mentioned organic photoelectrical material, the organic photoelectrical material is organic for making Electroluminescent device, organic solar batteries or organic field effect tube.
The present invention also provides a kind of organic electroluminescence devices, are passed by glass substrate, anode, hole injection layer, hole Defeated layer, luminescent layer, electron transfer layer, electron injecting layer and cathode stack gradually, or by glass substrate, anode, hole Implanted layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode and photosphere stacks gradually out, wherein The luminescent layer, the electron transfer layer and/or the photosphere out include at least above-mentioned organic photoelectrical material.
The present invention forms a kind of thermotropic delayed fluorescence material using phenanthro- imidazoles and triazine as basic structural unit.To electricity The stronger triazine group of sub- property, imidazole group are even or thick and form part rigidifying with the phenanthryl group key with larger conjugate planes Donor-receptor type molecular structure, reduce nonradiative transition caused by excitation state vibration relaxation, be effectively improved device drop rolling, Meanwhile molecular distortion degree is strengthened in the further modification of electron-withdrawing stronger functional groups, forms Intramolecular electron transfer Configuration effectively reduces the overlapping of HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital), and then effectively subtracts Small singlet state-triplet energy gap assigns the synergistic effect of material high exciton utilization rate and high fluorescent radiation efficiency, improves device The exciton transfer and luminescent properties of device under high current density.Use organic photoelectrical material provided by the invention as shine Layer material, electron transport material, the organic electroluminescence device for going out the preparation of photosphere material, light emission luminance is high, and external quantum efficiency is high, Driving voltage is low, can effectively improve the rolling of device drop and nonradiative transition, issues pure dark blue coloured light, is a kind of excellent OLED Material.
Detailed description of the invention
Fig. 1 is the device energy diagram of compound 144；
The voltage-that Fig. 2, which is compound 144, prepares device as luminescent layer guest materials and without the compounds of this invention is bright Spend performance diagram；
The voltage-that Fig. 3, which is compound 144, prepares device as luminescent layer guest materials and without the compounds of this invention is bright Spend performance diagram；
Fig. 4 is the electric current effect that compound 144 prepares device as luminescent layer guest materials and without the compounds of this invention Rate-current density characteristics curve graph.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.According to the technical essence of the invention to following embodiment institute Any simple modification, equivalent variations for making etc., still fall within the protection scope of technical solution of the present invention.The present invention is not limited to following realities Apply content described in example.
Embodiment 1
Compound 3 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), uncle 4- is added Butyl phenyl boric acid (35.60g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethyl alcohol 75mL, water 75mL, In N2Protection is lower to be added tetrakis triphenylphosphine palladium (0.35g, 3mmol), and reaction controlling reacts 12h at 85 DEG C, and liquid phase monitoring is anti- It should complete.It is cooled to room temperature, washes twice, active carbon decoloring is added, filtering is concentrated to give faint yellow solid, ethyl alcohol recrystallization two All over product, dry 4,6- bis- (4- tert-butyl-phenyl) -1,3,5-triazines -2- amine 32.44g, yield 90% under vacuum.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), 4,6- bis- (4- tert-butyl-phenyl) -1,3 is added, 5- triazine -2- amine (21.63g, 60mmol), 4- tolyl aldehyde (9.73g, 60mmol), ammonium acetate (7.71g, 100mmol) It is dissolved in the glacial acetic acid of 250mL and adds to reactor, under nitrogen atmosphere, be warming up to 115 DEG C of reaction 8h, liquid phase monitoring has been reacted At.It is cooled to room temperature, is washed with water twice, active carbon decoloring is added, filters, is concentrated, twice of re-crystallizing in ethyl acetate, under vacuum Target compound 30.18g, yield 87% can be obtained in drying.Characterization of compound is as follows: mass spectrograph MALDI-TOF-MS (m/z) =693.9395, theoretical molecular weight 693.9390；Anal.Calcd for C48H47N5(%): C 83.08, H 6.83, N 10.09Found:C 83.10,H 6.84,N 10.06。
Embodiment 2
Compound 12 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, addition 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), (9, 9- dimethyl -9H- fluorenes -2- base) boric acid (47.62g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, second Alcohol 75mL, water 75mL, in N2Protection is lower to be added tetrakis triphenylphosphine palladium (0.35g, 3mmol), and reaction controlling is at 85 DEG C, reaction 12h, liquid phase monitoring reaction are completed.It is cooled to room temperature, washes twice, active carbon decoloring is added, filtering is concentrated to give pale yellow colored solid Body, twice of product of ethyl alcohol recrystallization, dry 4,6- bis- (9,9- methyl-9 H-fluorene -2- base) -1,3,5-triazines -2- under vacuum Amine 42.29g, yield 88%.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), (9, the 9- methyl-9 H-fluorene -2- of 4,6- bis- is added Base) -1,3,5-triazines -2- amine (28.84g, 60mmol), benzaldehyde (6.37g, 60mmol), ammonium acetate (7.71g, It 100mmol) is dissolved in the glacial acetic acid of 250mL and adds to reactor, under nitrogen atmosphere, be warming up to 115 DEG C of reaction 8h, liquid phase prison Reaction is surveyed to complete.It is cooled to room temperature, is washed with water twice, active carbon decoloring is added, filters, concentration, re-crystallizing in ethyl acetate two Time, target compound 32.21g, yield 85% can be obtained in drying under vacuum.Characterization of compound is as follows: mass spectrograph MALDI- TOF-MS (m/z)=757.9417, theoretical molecular weight 757.9410；Anal.Calcd for C54H39N5(%): C 85.57, H 5.19,N 9.24Found:C 85.54,H 5.20,N 9.26。
Embodiment 3
Compound 21 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), benzene boron is added Acid (24.39g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethyl alcohol 75mL, water 75mL, in N2Protection Lower addition tetrakis triphenylphosphine palladium (0.35g, 3mmol), reaction controlling react 12h at 85 DEG C, and liquid phase monitoring reaction is completed.It is cold But it to room temperature, washes twice, is added active carbon decoloring, filtering is concentrated to give faint yellow solid, twice of product of ethyl alcohol recrystallization, very Dry 4,6- diphenyl -1,3,5-triazines -2- amine 22.35g, yield 90% under sky.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), 4,6- diphenyl -1,3,5-triazines -2- amine is added (14.89g, 60mmol), [1,1'- biphenyl] -4- formaldehyde (10.93g, 60mmol), ammonium acetate (7.71g, 100mmol) dissolution Reactor is added in the glacial acetic acid of 250mL, under nitrogen atmosphere, is warming up to 115 DEG C of reaction 8h, liquid phase monitoring reaction is completed. It is cooled to room temperature, is washed with water twice, active carbon decoloring is added, filters, is concentrated, twice of re-crystallizing in ethyl acetate, is done under vacuum It is dry that target compound 26.17g, yield 87% can be obtained.Characterization of compound is as follows: mass spectrograph MALDI-TOF-MS (m/z)= 601.7135 theoretical molecular weight 601.7130；Anal.Calcd for C42H27N5(%): C 83.84, H 4.52, N 11.64Found:C 83.85,H 4.55,N 11.60。
Embodiment 4
Compound 40 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), (two is added Benzofuran -2- base) boric acid (42.40g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethyl alcohol 75mL, water 75mL, in N2Protection is lower to be added tetrakis triphenylphosphine palladium (0.35g, 3mmol), and reaction controlling reacts 12h at 85 DEG C, Liquid phase monitoring reaction is completed.It is cooled to room temperature, washes twice, active carbon decoloring is added, filtering is concentrated to give faint yellow solid, second Alcohol recrystallizes twice of product, dry 4,6- bis- (dibenzofurans -2- base) -1,3,5-triazines -2- amine 37.27g under vacuum, Yield 87%.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), 4,6- bis- (dibenzofurans -2- base) -1 is added, 3,5- triazine -2- amine (25.71g, 60mmol), [1,1'- biphenyl] -3- formaldehyde (10.93g, 60mmol), ammonium acetate (7.71g, It 100mmol) is dissolved in the glacial acetic acid of 250mL and adds to reactor, under nitrogen atmosphere, be warming up to 115 DEG C of reaction 8h, liquid phase prison Reaction is surveyed to complete.It is cooled to room temperature, is washed with water twice, active carbon decoloring is added, filters, concentration, re-crystallizing in ethyl acetate two Time, target compound 33.23g, yield 85% can be obtained in drying under vacuum.Characterization of compound is as follows: mass spectrograph MALDI- TOF-MS (m/z)=781.8748, theoretical molecular weight 781.8750； Anal.Calcd for C54H31N5O2(%): C 82.95,H 4.00,N 8.96Found:C 82.91,H 4.06,N 8.94。
Embodiment 5
Compound 58 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), (naphthalene-is added 2- yl) boric acid (34.40g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethyl alcohol 75mL, water 75mL, N2Protection is lower to be added tetrakis triphenylphosphine palladium (0.35g, 3mmol), and reaction controlling reacts 12h, liquid phase monitoring reaction at 85 DEG C It completes.It being cooled to room temperature, washes twice, be added active carbon decoloring, filtering is concentrated to give faint yellow solid, and twice of ethyl alcohol recrystallization Product, dry 4,6- bis- (naphthalene -2- base) -1,3,5-triazines -2- amine 30.66g, yield 88% under vacuum.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), 4,6- bis- (naphthalene -2- base) -1,3,5- tri- is added Piperazine -2- amine (20.90g, 60mmol), 2- naphthaldehyde (9.37g, 60mmol), ammonium acetate (7.71g, 100mmol) are dissolved in Reactor is added in the glacial acetic acid of 250mL, under nitrogen atmosphere, is warming up to 115 DEG C of reaction 8h, liquid phase monitoring reaction is completed.It is cold But it to room temperature, is washed with water twice, active carbon decoloring is added, filters, is concentrated, twice of re-crystallizing in ethyl acetate, it is dry under vacuum Target compound 28.04g, yield 83% can be obtained.Characterization of compound is as follows: mass spectrograph MALDI-TOF-MS (m/z)= 675.7955 theoretical molecular weight 675.7950；Anal.Calcd for C48H29N5(%): C 85.31, H 4.33, N 10.36Found:C 85.33,H 4.34,N 10.33。
Embodiment 6
Compound 68 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), (hexichol is added Bithiophene -1- base) boric acid (45.61g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethyl alcohol 75mL, Water 75mL, in N2Protection is lower to be added tetrakis triphenylphosphine palladium (0.35g, 3mmol), and reaction controlling reacts 12h, liquid phase at 85 DEG C Monitoring reaction is completed.It is cooled to room temperature, washes twice, active carbon decoloring is added, filtering is concentrated to give faint yellow solid, ethyl alcohol weight Crystallize twice of product, dry 4,6- bis- (dibenzothiophenes -1- base) -1,3,5-triazines -2- amine 40.07g, yield under vacuum 87%.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), 4,6- bis- (dibenzothiophenes -1- base) -1 is added, 3,5- triazine -2- amine (27.63g, 60mmol), 2- naphthaldehyde (9.37g, 60mmol), ammonium acetate (7.71g, 100mmol) are molten Solution adds to reactor in the glacial acetic acid of 250mL, under nitrogen atmosphere, is warming up to 115 DEG C of reaction 8h, liquid phase monitoring has been reacted At.It is cooled to room temperature, is washed with water twice, active carbon decoloring is added, filters, is concentrated, twice of re-crystallizing in ethyl acetate, under vacuum Target compound 33.31g, yield 82% can be obtained in drying.Characterization of compound is as follows: mass spectrograph MALDI-TOF-MS (m/z) =787.9587, theoretical molecular weight 787.9590；Anal.Calcd for C52H29N5S2(%): C 79.26, H 3.71, N 8.89Found:C 79.25,H 3.76,N 8.85。
Embodiment 7
Compound 86 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), benzene boron is added Acid (24.39g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethyl alcohol 75mL, water 75mL, in N2Protection Lower addition tetrakis triphenylphosphine palladium (0.35g, 3mmol), reaction controlling react 12h at 85 DEG C, and liquid phase monitoring reaction is completed.It is cold But it to room temperature, washes twice, is added active carbon decoloring, filtering is concentrated to give faint yellow solid, twice of product of ethyl alcohol recrystallization, very Dry 4,6- diphenyl -1,3,5-triazines -2- amine 22.35g, yield 90% under sky.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), 4,6- diphenyl -1,3,5- triazine -2- is added Amine (14.89g, 60mmol), 4- diphenylamines benzaldehyde (16.40g, 60mmol), ammonium acetate (7.71g, 100mmol) are dissolved in Reactor is added in the glacial acetic acid of 250mL, under nitrogen atmosphere, is warming up to 115 DEG C of reaction 8h, liquid phase monitoring reaction is completed.It is cold But it to room temperature, is washed with water twice, active carbon decoloring is added, filters, is concentrated, twice of re-crystallizing in ethyl acetate, it is dry under vacuum Target compound 29.79g, yield 86% can be obtained.Characterization of compound is as follows: mass spectrograph MALDI-TOF-MS (m/z)= 692.8264 theoretical molecular weight 692.8260；Anal.Calcd for C48H32N6(%): C 83.21, H 4.66, N 12.13Found:C 83.23,H 4.64,N 12.13。
Embodiment 8
Compound 114 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), benzene boron is added Acid (24.39g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethyl alcohol 75mL, water 75mL, in N2Protection Lower addition tetrakis triphenylphosphine palladium (0.35g, 3mmol), reaction controlling react 12h at 85 DEG C, and liquid phase monitoring reaction is completed.It is cold But it to room temperature, washes twice, is added active carbon decoloring, filtering is concentrated to give faint yellow solid, twice of product of ethyl alcohol recrystallization, very Dry 4,6- diphenyl -1,3,5-triazines -2- amine 22.35g, yield 90% under sky.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), 4,6- diphenyl -1,3,5-triazines -2- amine is added (14.89g, 60mmol), 9- (3- aldehyde radical phenyl) -9H- carbazole (16.22g, 60mmol), ammonium acetate (7.71g, 100mmol) It is dissolved in the glacial acetic acid of 250mL and adds to reactor, under nitrogen atmosphere, be warming up to 115 DEG C of reaction 8h, liquid phase monitoring has been reacted At.It is cooled to room temperature, is washed with water twice, active carbon decoloring is added, filters, is concentrated, twice of re-crystallizing in ethyl acetate, under vacuum Target compound 29.70g, yield 86% can be obtained in drying.Characterization of compound is as follows: mass spectrograph MALDI-TOF-MS (m/z) =690.8104, theoretical molecular weight 690.8100；Anal.Calcd for C48H30N6(%): C 83.46, H 4.38, N 12.17Found:C 83.43,H 4.41,N 12.16。
Embodiment 9
Compound 127 provided by the present invention can be synthesized by following method.
(1) in 500ml there-necked flask, addition 4,6-, bis- chloro-1,3,5-triazines -2- amine (16.50g, 100mmol), [1, 1'- phenyl] -3- ylboronic acid (39.60g, 200mmol), potassium carbonate (27.64g, 200mmol), toluene 150mL, ethyl alcohol 75mL, Water 75mL, in N2Protection is lower to be added tetrakis triphenylphosphine palladium (0.35g, 3mmol), and reaction controlling reacts 12h, liquid phase at 85 DEG C Monitoring reaction is completed.It is cooled to room temperature, washes twice, active carbon decoloring is added, filtering is concentrated to give faint yellow solid, ethyl alcohol weight Crystallize twice of product, dry 4,6- bis- ([1,1'- biphenyl] -3- base) -1,3,5-triazines -2- amine 35.24g, yield under vacuum 88%.
(2) in 500ml there-necked flask, phenanthrenequione (10.41g, 50mmol), 4,6- bis- ([1,1'- biphenyl] -3- base)-is added 1,3,5-triazines -2- amine (24.03g, 60mmol), 4- (naphthalene -2- base) benzaldehyde (13.94g, 60mmol), ammonium acetate (7.71g, 100mmol), which is dissolved in the glacial acetic acid of 250mL, adds to reactor, under nitrogen atmosphere, is warming up to 115 DEG C of reactions 8h, liquid phase monitoring reaction are completed.It is cooled to room temperature, is washed with water twice, active carbon decoloring is added, filters, concentration, ethyl acetate It recrystallizes twice, target compound 33.77g, yield 84% can be obtained in drying under vacuum.Characterization of compound is as follows: mass spectrograph MALDI-TOF-MS (m/z)=803.9695, theoretical molecular weight 803.9690； Anal.Calcd for C58H37N5(%): C 86.65,H 4.64,N 8.71Found:C 86.67,H 4.65,N 8.68。
Embodiment 10
In the present embodiment, compound is prepared for multiple organic as the luminescent layer guest materials in organic electroluminescence device Electroluminescent device, structure are substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/electron injecting layer (EI)/cathode,
Substrate is glass substrate, and anode is tin indium oxide (ITO), and hole injection layer is molybdenum trioxide (MoO3), hole passes Defeated layer is 4,4', 4, and "-three (carbazole -9- base) triphenylamines (TCTA), organic luminous layer material of main part are two [2- ((oxo) hexichol Base phosphino-) phenyl] ether (DPEPO), organic luminous layer guest materials is compound 3 provided by the present invention, compound 12, chemical combination Object 21, compound 40, compound 58, compound 68, compound 86, compound 114, compound 127, electron transfer layer 3, 3'- [5'- [3- (3- pyridyl group) phenyl] [1,1':3', 1 "-terphenyl] -3,3 "-diyl] two pyridines (TmPyPb), electronics note Entering layer is lithium fluoride (LiF), and cathode is aluminium (Al).
Then ito glass is dried in vacuo 2 hours in succession in cleaning agent and deionized water with ultrasonic cleaning 30 minutes (105 DEG C), then ito glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, it is transmitted to system in vacuum chamber Standby organic film and metal electrode then prepare the MoO of one layer of 10nm by the method being evaporated in vacuo3, then it is deposited 60nm's Then TCTA continues through the present invention containing 5% (as mass fraction) of one layer of 12nm in vacuum evaporation on this basis The TmPyPb of one layer of 15nm, the Al of the LiF and 100nm of 1nm is finally deposited in the DPEPO of compound again.
Organic electroluminescence device performance see the table below:
The further modification of electron-withdrawing stronger functional groups enhances phenanthro- it can be seen from upper table and Fig. 1 Imidazoles connects the degreeof tortuosity of triazine molecular configuration, and Intramolecular electron transfer effectively reduces compound HOMO-LUMO, and (highest occupies Molecular orbit-lowest unoccupied molecular orbital) overlapping, and then singlet state-triplet energy gap is effectively reduced, so that with glass base Plate/ITO/MoO3/ TCTA/DPEPO:5%wt compound 144/TmPyPb/LiF/Al is each functional layer of device of structure preparation Storeroom level-density parameter degree is more preferable, the energy transfer of luminescent layer Subjective and Objective storeroom and higher in conjunction with launching efficiency.
The device prepared it can be seen from upper table and Fig. 2 are into Fig. 4 and without containing organic photoelectrical material provided by the invention Part is compared, and organic photoelectrical material provided by the present invention is starting voltage, shining as device prepared by luminescent layer guest materials There is significant progress in terms of brightness, current efficiency, luminous efficiency and external quantum efficiency, the nonradiative transition and drop rolling of device are asked Topic is effectively improved.
Embodiment 11
In the present embodiment, compound prepares multiple Organic Electricities as the luminescent layer material of main part in organic electroluminescence device Electroluminescence device, structure be substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/ Electron transfer layer (ETL)/electron injecting layer (EI)/cathode,
Substrate is glass substrate, and anode is tin indium oxide (ITO), and hole injection layer is molybdenum trioxide (MoO3), hole passes Defeated layer is 4,4', 4, and "-three (carbazole -9- base) triphenylamines (TCTA), organic luminous layer material of main part are provided by the present inventionization Close object 3, compound 21, compound 86, compound 127, organic luminous layer guest materials be it is bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium (Firpic), electron transfer layer 3,3'- [5'- [3- (3- pyridyl group) phenyl] [1,1':3', 1 "-three Biphenyl] -3,3 "-diyl] two pyridines (TmPyPb), electron injecting layer is lithium fluoride (LiF), and cathode is aluminium (Al).
Then ito glass is dried in vacuo 2 hours in succession in cleaning agent and deionized water with ultrasonic cleaning 30 minutes (105 DEG C), then ito glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, it is transmitted to system in vacuum chamber Standby organic film and metal electrode then prepare the MoO of one layer of 10nm by the method being evaporated in vacuo3, then it is deposited 60nm's Then TCTA continues through the Firpic containing 5% (as mass fraction) of one layer of 12nm in vacuum evaporation on this basis Compound provided by the invention, the TmPyPb of one layer of 15nm, the Al of the LiF and 100nm of 1nm are finally deposited again.
Organic electroluminescence device performance see the table below:
As can be seen from the above table, compared with the device without containing organic photoelectrical material provided by the invention preparation, the present invention Provided organic photoelectrical material is a kind of ideal luminescent layer material of main part, intensive donor-receptor moiety combinations be electronics, The injection in both holes provides access, is obviously improved device in starting voltage, current efficiency, luminous efficiency and outer quantum effect Performance in terms of rate, the nonradiative transition of device and drop rolling problem are effectively improved.
Embodiment 12
In the present embodiment, compound prepares multiple organic electroluminescences as the electron transport material in organic electroluminescence device Luminescent device, structure are substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electricity Sub- transport layer (ETL)/electron injecting layer (EI)/cathode,
Substrate is glass substrate, and anode is tin indium oxide (ITO), and hole injection layer is molybdenum trioxide (MoO3), hole passes Defeated layer is 4,4', 4, and "-three (carbazole -9- base) triphenylamines (TCTA), organic luminous layer material of main part are two [2- ((oxo) hexichol Base phosphino-) phenyl] ether (DPEPO), organic luminous layer guest materials is bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction Iridium (Firpic), electron transfer layer are compound 3 provided by the present invention, compound 21, compound 40, compound 58, electronics Implanted layer is lithium fluoride (LiF), and cathode is aluminium (Al).
Then ito glass is dried in vacuo 2 hours in succession in cleaning agent and deionized water with ultrasonic cleaning 30 minutes (105 DEG C), then ito glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, it is transmitted to system in vacuum chamber Standby organic film and metal electrode then prepare the MoO of one layer of 10nm by the method being evaporated in vacuo3, then it is deposited 60nm's Then TCTA continues through the Firpic containing 5% (as mass fraction) of one layer of 12nm in vacuum evaporation on this basis DPEPO, the compound provided by the invention of one layer of 15nm, the Al of the LiF and 100nm of 1nm are finally deposited again.
Organic electroluminescence device performance see the table below:
As can be seen from the above table, compared with the device without containing organic photoelectrical material provided by the invention preparation, the present invention Provided organic photoelectrical material is a kind of ideal electron transport material, and electron transfer rate and hole transport rate are effectively flat Weighing apparatus, improves exciton non-composite consumption problem, has been obviously improved device in terms of starting voltage, current efficiency, luminous efficiency Performance.
Embodiment 13
In the present embodiment, compound prepares multiple organic electroluminescences as the photosphere that goes out in organic electroluminescence device Part, structure are substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electron-transport Layer (ETL)/electron injecting layer (EI)/cathode/go out photosphere,
Substrate is glass substrate, and anode is tin indium oxide (ITO), and hole injection layer is molybdenum trioxide (MoO3), hole passes Defeated layer is 4,4', 4, and "-three (carbazole -9- base) triphenylamines (TCTA), organic luminous layer material of main part are two [2- ((oxo) hexichol Base phosphino-) phenyl] ether (DPEPO), organic luminous layer guest materials is bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction Iridium (Firpic), electron transfer layer 3,3'- [5'- [3- (3- pyridyl group) phenyl] [1,1':3', 1 "-terphenyl] -3,3 " - Diyl] two pyridines (TmPyPb), electron injecting layer is lithium fluoride (LiF), and cathode is aluminium (Al), and photosphere provides out for the present invention Compound 3, compound 21, compound 58, compound 114.
Then ito glass is dried in vacuo 2 hours in succession in cleaning agent and deionized water with ultrasonic cleaning 30 minutes (105 DEG C), then ito glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, it is transmitted to system in vacuum chamber Standby organic film and metal electrode then prepare the MoO of one layer of 10nm by the method being evaporated in vacuo3, then it is deposited 60nm's Then TCTA continues through the Firpic containing 5% (as mass fraction) of one layer of 12nm in vacuum evaporation on this basis DPEPO, the TmPyPb of one layer of 15nm, provided by the present inventionization of the Al and 15nm of the LiF of 1nm, 100nm are finally deposited again Close object.
Organic electroluminescence device performance see the table below:
As can be seen from the above table, compared with the device without containing organic photoelectrical material provided by the invention preparation, the present invention Provided organic photoelectrical material is a kind of ideal photosphere material out, reduces the loss of light between interface, effectively improves device Light extraction efficiency, be obviously improved performance of the device in terms of luminous efficiency, external quantum efficiency.
Embodiment 14
In the present embodiment, the organic electroluminescence device of preparation is free of compound provided by the present invention, and structure is base Piece/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/electronics Implanted layer (EI)/cathode, substrate are glass substrate, and anode is tin indium oxide (ITO), and hole injection layer is molybdenum trioxide (MoO3), "-three (carbazole -9- base) triphenylamines (TCTA), organic luminous layer material of main part are two to hole transmission layer 4,4', 4 [2- ((oxo) diphenylphosphino) phenyl] ether (DPEPO), organic luminous layer guest materials are bis- (4,6- difluorophenyl pyridinatos- N,C2) pyridinecarboxylic conjunction iridium (Firpic), electron transfer layer 3,3'- [5'- [3- (3- pyridyl group) phenyl] [1,1':3', 1 "-terphenyl] -3,3 "-diyl] two pyridines (TmPyPb), electron injecting layer is lithium fluoride (LiF), and cathode is aluminium (Al).
Then ito glass is dried in vacuo 2 hours in succession in cleaning agent and deionized water with ultrasonic cleaning 30 minutes (105 DEG C), then ito glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, it is transmitted to system in vacuum chamber Standby organic film and metal electrode then prepare the MoO of one layer of 10nm by the method being evaporated in vacuo3, then it is deposited 60nm's Then TCTA continues through the Firpic containing 5% (as mass fraction) of one layer of 12nm in vacuum evaporation on this basis DPEPO, the TmPyPb of one layer of 15nm, the Al of the LiF and 100nm of 1nm are finally deposited again.
Organic electroluminescence device performance see the table below:
Although the present invention is described in conjunction with the embodiments, the present invention is not limited to the above embodiments, should manage Solution, under the guidance of present inventive concept, any modification, equivalent replacement, improvement and so on should be included in protection of the invention Within the scope of.

Claims (10)

1. a kind of organic photoelectrical material, which is characterized in that the material is to introduce function using phenanthro- imidazoles and triazine as structural unit The compound that energy property group is constituted, general structure such as following structural:
Wherein, R1、R2For substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C5-C60Heteroaryl perfume base in Any one；
R3For hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C5-C60 Heteroaryl perfume base, any one in substituted or unsubstituted amido；
R1、R2、R3It is identical or different.
2. organic photoelectrical material according to claim 1, which is characterized in that the R1And R2Under being substituted or unsubstituted Any one in column group:
Wherein, * is the site connecting with triazine structure.
3. organic photoelectrical material according to claim 2, which is characterized in that the R1And R2It is identical.
4. organic photoelectrical material according to any one of claims 1 to 3, which is characterized in that R3 is hydrogen, substituted or unsubstituted Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted xenyl, substituted or unsubstituted naphthalene, substitution or do not take Any one in the carbazyl in generation, substituted or unsubstituted hexichol amido, wherein singly-bound between the R3 and the phenyl ring of connection It is connected or directly condensed.
5. a kind of preparation method such as the described in any item organic photoelectrical materials of Claims 1-4, which is characterized in that including with Lower route:
Step 1:
Step 2:
Wherein, R1、R2For substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C5-C60Heteroaryl perfume base in Any one；
R3For hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted C6-C60Aromatic radical, substituted or unsubstituted C5-C60 Heteroaryl perfume base, any one in substituted or unsubstituted amido；
R1、R2、R3It is identical or different.
6. preparation method according to claim 5, which is characterized in that the alkali in the first step is potassium carbonate, carbon One of sour sodium or cesium carbonate, the solvent be one of toluene, dimethylbenzene, n,N-dimethylacetamide, ethyl alcohol, water or A variety of, the catalyst is one of tetrakis triphenylphosphine palladium, palladium acetate, copper acetate.
7. preparation method according to claim 6, which is characterized in that in the first step, 4,6- bis- chloro- 1,3,5- tri- Piperazine -2- amine contains R1The boronic acid derivatives of substituent group contain R2The boronic acid derivatives of substituent group, catalyst, alkali are according to molar ratio 1:1: 1:2 ‰ -5 ‰: 2-4 feeds intake；The solvent includes toluene, second alcohol and water, and the volume ratio of the toluene, ethyl alcohol, water is 2:1: 1；At 60 DEG C -100 DEG C, the reaction time is 4-36 hours for reaction temperature control.
8. preparation method according to claim 5, which is characterized in that in the second step, R1、R2Corresponding 1,3 replaced, 5- triazine -2- amine derivative, R3The corresponding benzaldehyde derivative replaced, phenanthrenequione, ammonium acetate are according to molar ratio 1:1-1.5:1- 1.5:2-4 feeding intake；Reaction temperature is controlled at 80-120 DEG C；Reaction time is 4-12h.
9. a kind of application of such as described in any item organic photoelectrical materials of Claims 1-4, which is characterized in that organic light Electric material is for making organic electroluminescence device, organic solar batteries or organic field effect tube.
10. a kind of organic electroluminescence device, by glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electronics Transport layer, electron injecting layer and cathode stack gradually, or by glass substrate, anode, hole injection layer, hole transport Layer, luminescent layer, electron transfer layer, electron injecting layer, cathode and photosphere stacks gradually out, which is characterized in that described to shine Layer, the electron transfer layer and/or the photosphere out include at least such as the described in any item organic photoelectric materials of Claims 1-4 Material.
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