CN114957144A - Bipolar host material and preparation method and application thereof - Google Patents

Bipolar host material and preparation method and application thereof Download PDF

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CN114957144A
CN114957144A CN202210710606.9A CN202210710606A CN114957144A CN 114957144 A CN114957144 A CN 114957144A CN 202210710606 A CN202210710606 A CN 202210710606A CN 114957144 A CN114957144 A CN 114957144A
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triphenylphosphine
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唐本忠
赵祖金
于茂兴
吴星
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South China University of Technology SCUT
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    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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Abstract

The invention belongs to the technical field of organic photoelectric functional materials, and discloses a bipolar main body material and a preparation method and application thereof. The preparation method of the main body material comprises the following steps: s1, mixing halogenated hydrocarbon, an electron-donating aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and a mixed solvent, and then carrying out substitution reaction to obtain a bromine-substituted compound; and S2, mixing a bromine substituted compound, an electron-withdrawing aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and a mixed solvent, and then carrying out substitution reaction to obtain the bipolar main body material. The bipolar main body material prepared by the invention has higher triplet state energy level, and the thermal decomposition temperature and the glass transition temperature of the bipolar main body material are high, thereby being beneficial to the stable operation of the organic light-emitting diode and prolonging the service life.

Description

Bipolar host material and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic photoelectric functional materials, in particular to a bipolar main body material and a preparation method and application thereof.
Background
A display screen of an organic electroluminescent diode (OLED) has many advantages of low power consumption due to low driving voltage, high brightness, high color gamut due to full color light emission, high contrast due to self-luminescence, high refresh rate due to fast response, and the like. In recent years, the development of the OLED is becoming mature, and occupies a considerable market share in terms of small-sized display panels such as mobile phone screens, and with the development and maturation of the solution processing technology, the OLED is also having competitive advantages in terms of large-sized display panels, flexible devices, and illumination. At present, a considerable number of high performance OLED devices (ACS Materials Letters,2019,1(6): 613-.
The adoption of the doped host-guest light emitting layer structure is an important means for improving the performance of the OLED at present, and the selection of proper host materials and guest materials can improve the performance of the device to the maximum extent. In order to minimize the energy loss during exciton transport, the host material needs to be designed to meet several requirements. First, the host material should have a high thermal decomposition temperature to accommodate the evaporation process and a high glass transition temperature to prevent interface separation, thereby increasing the lifetime of the device. Second, it should have a balanced carrier transport capability to make the electron hole recombine in the light-emitting layer as much as possible, and prevent the serious efficiency roll-off of the polarization of the host molecule caused by too high charge concentration. Third, T of host Material 1 The energy level is sufficiently high, depending on the T of the guest material to be dispersed 1 Energy level, which avoids the reverse energy transfer from the guest molecule to the host molecule and ensures the exciton to emit light compositely on the guest. However, there has been no mature theoretical study and practical application of aromatic ring derivative groups for use in preparing host materials.
Therefore, how to provide a high performance host material containing aromatic ring derivative group is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of this, the invention provides a bipolar host material, a preparation method and an application thereof. According to the invention, the aromatic ring derivative group is introduced into the bipolar main body material, so that the bipolar main body material has balanced carrier transmission performance and higher triplet state energy level, is applied to the organic electroluminescent diode, is beneficial to stable operation of the organic electroluminescent diode, and prolongs the service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a bipolar host material, which has one of the structures shown in the following general formulas 1-3:
Figure BDA0003707821420000021
Figure BDA0003707821420000031
wherein Ar is 1 Independently an electron-donating aromatic ring derivative group, Ar 2 Independently an electron-withdrawing aromatic ring derivative group;
R 1 、R 2 、R 3 、R 4 、R 5 and R 6 Independently hydrogen, methyl or phenyl.
The invention provides a preparation method of the bipolar host material, which comprises the following steps:
s1, mixing halogenated hydrocarbon, an electron-donating aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and a mixed solvent, and then carrying out substitution reaction to obtain a bromine substituted compound;
s2, mixing a bromine substituted compound, an electron-withdrawing aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and a mixed solvent, and then carrying out substitution reaction to obtain a bipolar main body material;
the halogenated hydrocarbon is bromoiodobenzene, bromoiodobiphenyl or dibrombinaphthyl.
Further, the temperature of the substitution reaction in the step S1 and the step S2 is independently 90-120 ℃, and the time is independently 6-24 hours.
Further, the mixed solvent in the step S1 and the step S2 is a mixture of toluene, ethanol and water, wherein the volume ratio of toluene, ethanol and water is 2-9: 1: 1 to 2.
Further, the electron-donating aromatic boric acid derivative is one of 4- (9 hydrogen-carbazole-9-yl) phenylboronic acid, (4- (3, 6-di-tert-butyl-9 hydrogen-carbazole-9-yl) phenyl) boric acid, 4-boric acid triphenylamine and boron- [4- (3, 6-diphenyl-9 hydrogen-carbazole-9-yl) phenyl ] boric acid.
Further, the electron-withdrawing aromatic boronic acid derivative is 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) yl-1, 3, 5-triazine or (4- (4, 6-diphenylpyrimidin-2-yl) phenyl) boronic acid.
Further, the molar volume ratio of the halogenated hydrocarbon, the electron-donating aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and the mixed solvent is 1 mmol: 1-4 mmol: 3-5 mmol: 0.02-0.05 mmol: 2.5-5 mL.
Further, the molar volume ratio of the bromine-substituted compound, the electron-withdrawing aromatic boronic acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and the mixed solvent is 1 mmol: 1-4 mmol: 3-5 mmol: 0.02-0.05 mmol: 2.5-5 mL.
The invention also provides application of the bipolar host material in an organic electroluminescent diode.
The principle applied by the invention is as follows: the electron-withdrawing aromatic ring derivative group in the bipolar main body material provided by the invention has better planarity, and the electron transmission performance of the bipolar main body material is ensured; then, the hole transmission performance of the semiconductor material is optimized by introducing a proper electron-donating aromatic ring derivative group, so that the formed intramolecular charge transfer state intensity is not large, blue light emission is ensured, and effective generation between a host and an object is facilitated
Figure BDA0003707821420000041
Resonance energy transfer and balancing the carrier transport capability of the bipolar host material; the used electron-donating aromatic ring derivative group has a high triplet state energy level, so that the reverse transfer of energy from an object to a host in electroluminescence is avoided; at the same time, a greater molecular weight holdThe thermal stability and the morphology stability of the bipolar host material are proved, and the phase separation of a host and an object in electroluminescence is avoided. The photophysical properties and energy level characteristics of the bipolar main material can be regulated and controlled by modifying the electron-donating aromatic ring derivative group.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the bipolar main body material prepared by the invention has higher triplet state energy level, and the thermal decomposition temperature and the glass transition temperature of the bipolar main body material are high, so that the stable operation of the organic light-emitting diode is facilitated, and the service life is prolonged;
2. the bipolar main material prepared by the invention has balanced hole and electron transmission capability, ensures the effective combination of excitons in a luminescent layer, has good stability and film forming property, can be used for preparing a device by vacuum evaporation film forming, and has flexible selection of the device preparation process;
3. the bipolar main body material prepared by the invention has the advantages of simple synthesis, higher yield and stable structure;
4. the bipolar main body material prepared by the invention is used in an organic electroluminescent diode, and has the advantages of high device efficiency, small roll-off and excellent performance.
Drawings
FIG. 1 is a graph of luminance-voltage-current density for an OLED device prepared using the bipolar host material of example 1;
FIG. 2 is the electroluminescence spectrum of an OLED device prepared using the bipolar host material of example 1;
FIG. 3 is a graph of luminance-voltage-current density for an OLED device prepared using the bipolar host material of example 7;
FIG. 4 is the electroluminescence spectrum of an OLED device prepared using the bipolar host material of example 7;
FIG. 5 is a graph of luminance-voltage-current density for an OLED device prepared using the bipolar host material of example 13;
fig. 6 is an electroluminescence spectrum of an OLED device prepared using the bipolar host material in example 13.
Detailed Description
The invention provides a bipolar host material, which has one of the structures shown in the following general formulas 1-3:
Figure BDA0003707821420000061
wherein Ar is 1 Independently an electron-donating aromatic ring derivative group, Ar 2 Independently, an electron-withdrawing aromatic ring derivative group.
In the present invention, R 1 、R 2 、R 3 、R 4 、R 5 And R 6 Independently hydrogen, methyl or phenyl, preferably hydrogen or methyl, more preferably hydrogen.
In the present invention, the electron-donating aromatic ring derivative group is selected from any one of structures a1 to a12 shown below:
Figure BDA0003707821420000071
in the present invention, the electron-withdrawing aromatic ring derivative group is selected from any one of structures B1 to B12 shown below:
Figure BDA0003707821420000081
the invention provides a preparation method of the bipolar host material, which comprises the following steps:
s1, mixing halogenated hydrocarbon, an electron-donating aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and a mixed solvent, and then carrying out substitution reaction to obtain a bromine substituted compound;
and S2, mixing a bromine substituted compound, an electron-withdrawing aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and a mixed solvent, and then carrying out substitution reaction to obtain the bipolar main body material.
In the present invention, the halogenated hydrocarbon is bromoiodobenzene, bromoiodobiphenyl or dibromonaphthalene;
the bromoiodobenzene is preferably o-bromoiodobenzene or p-bromoiodobenzene, and is further preferably o-bromoiodobenzene;
the bromoiodobiphenyl is preferably 3-bromo-4-iodo-1, 1' -biphenyl or 2-iodo-5-bromobiphenyl; further preferably 3-bromo-4-iodo-1, 1' -biphenyl;
the dibromonaphthalene is preferably 1,8 dibromonaphthalene.
In the invention, the temperature of the substitution reaction in the step S1 and the step S2 is independently 90-120 ℃, preferably 95-110 ℃, and more preferably 100-105 ℃; the time is independent for 6-24 h, preferably 8-20 h, and further preferably 12-15 h.
In the invention, the mixed solvent in the step S1 and the step S2 is independently a mixture of toluene, ethanol and water, wherein the volume ratio of the toluene, the ethanol and the water is 2-9: 1: 1-2, preferably 3-7: 1: 1, more preferably 4 to 5: 1: 1.
in the present invention, the electron-donating aromatic boronic acid derivative is one of 4- (9-hydro-carbazol-9-yl) phenylboronic acid, (4- (3, 6-di-tert-butyl-9-hydro-carbazol-9-yl) phenyl) boronic acid, triphenylamine 4-boronic acid and boron- [4- (3, 6-diphenyl-9-hydro-carbazol-9-yl) phenyl ] boronic acid, preferably 4- (9-hydro-carbazol-9-yl) phenylboronic acid or (4- (3, 6-di-tert-butyl-9-hydro-carbazol-9-yl) phenyl) boronic acid, and more preferably 4- (9-hydro-carbazol-9-yl) phenylboronic acid.
In the present invention, the electron-withdrawing aromatic boronic acid derivative is 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) yl-1, 3, 5-triazine or (4- (4, 6-diphenylpyrimidin-2-yl) phenyl) boronic acid, preferably 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) yl-1, 3, 5-triazine.
In the invention, the molar volume ratio of the halogenated hydrocarbon, the electron-donating aromatic boric acid derivative, the potassium carbonate, the tetrakis (triphenylphosphine) palladium and the mixed solvent is 1 mmol: 1-4 mmol: 3-5 mmol: 0.02-0.05 mmol: 2.5-5 mL, preferably 1 mmol: 2-3 mmol: 4 mmol: 0.03-0.04 mmol: 3 to 4.5mL, more preferably 1 mmol: 2 mmol: 4 mmol: 0.04 mmol: 4 mL.
In the invention, the molar volume ratio of the bromine substituted compound, the electron-withdrawing aromatic boronic acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and the mixed solvent is 1 mmol: 1-4 mmol: 3-5 mmol: 0.02-0.05 mmol: 2.5-5 mL, preferably 1 mmol: 2-3 mmol: 4 mmol: 0.03-0.04 mmol: 3 to 4.5mL, more preferably 1 mmol: 2 mmol: 4 mmol: 0.04 mmol: 4 mL.
The invention also provides application of the bipolar host material in an organic electroluminescent diode.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000101
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of o-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 100 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 1-1 with the yield of 62%. HRMS (C) 24 H 16 BrN):m/z 397.0436。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 1-1, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 100 deg.C for 8 hr, and reacting with dichlorineExtracting with methane and water, concentrating, separating and purifying with silica gel column chromatography to obtain bipolar main material 1-2 with yield of 71%. 1 H NMR(500MHz,CDCl 3 ,δ)8.80–8.78(m,4H),8.75–8.72(m,2H),8.11(d,J＝7.7Hz,2H),7.64–7.53(m,10H),7.46–7.34(m,10H),7.25–7.22(m,2H)。HRMS(C 45 H 30 N 4 ):m/z 627.2548。
The bipolar host material 1-2 prepared in this example was used as a host material, and Ir (tptptpy) 2 The acac is an OLED device prepared from the guest luminescent material, and the device structure is as follows: ITO/HATCN (5nm)/TAPC (50nm)/TcTa (5nm)/3 wt% Ir (tptppy) 2 acac is 1-2(20nm)/TmPyPB (40nm)/LiF (1nm)/Al, and the device performance is tested.
The luminance-voltage-current density test results are shown in FIG. 1. from FIG. 1, the maximum luminance of the OLED device prepared by using the bipolar host material of this embodiment can be 103600cd/m 2 The starting voltage is as low as 2.9V.
Fig. 2 shows the electroluminescence spectrum of an OLED device prepared using the bipolar host material of this example.
Example 2
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000111
mixing 15mmol of (4- (3, 6-di-tert-butyl-9 hydro-carbazol-9-yl) phenyl) boric acid, 13.6mmol of o-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 90 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain bromine substituted compounds 1-3 with the yield of 64%. HRMS (C) 32 H 32 BrN):m/z 509.1790。
15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 1-3, and 40.9mmol of carbonMixing potassium and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing the reaction bottle for three times, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 90 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bipolar main material 1-4 with yield of 78%. HRMS (C) 53 H 46 N 4 ):m/z 738.3700。
Example 3
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000121
mixing 15mmol of 4-triphenylamine borate, 13.6mmol of o-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 95 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 1-5 with the yield of 78%. HRMS (C) 24 H 18 BrN):m/z399.0672。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) base-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 1-5, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing for three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 95 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bipolar main body material 1-6 with the yield of 76%. HRMS (C) 45 H 32 N 4 ):m/z 628.2654。
Example 4
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000131
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of 3-bromo-4-iodo-1, 1' -biphenyl, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 110 ℃ for reaction for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain bromine substituted compounds 1-7 with the yield of 66%. HRMS (C) 30 H 20 BrN):m/z 473.0800。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 1-7, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 110 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bipolar main material 1-8 with yield of 68%. HRMS (C) 51 H 34 N 4 ):m/z 702.8715。
Example 5
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000141
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of o-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 120 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 1-1 with the yield of 62%. HRMS (C) 24 H 16 BrN):m/z 397.0436。
15mmol of (4- (4, 6-diphenylpyrimidin-2-yl) phenyl) boronic acid, 13.6mmol of bromine-substituted compound 1-1, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium were mixed, and gas was evacuated three times in a reaction flask, and then 50mL of a mixed solvent in which the volume ratio of toluene, ethanol and water was 8: 1: 1. heating and refluxing at 120 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bipolar main material 1-10 with yield of 72%. HRMS (C) 46 H 31 N 3 ):m/z 625.7702。
Example 6
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000151
15mmol of boron- [4- (3, 6-diphenyl-9-hydro-carbazol-9-yl) phenyl]Mixing boric acid, 13.6mmol of o-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 115 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain bromine substituted compounds 1-10 with the yield of 59%. HRMS (C) 36 H 24 BrN):m/z 549.1011。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 1-10, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 115 deg.C for 8 hr, extracting with dichloromethane and water, concentrating, and separating and purifying by silica gel column chromatography to obtain bipolar main material 1-11 with yield of 68%. HRMS (C) 57 H 38 N 4 ):m/z 778.3048。
Example 7
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000152
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of p-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 100 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 2-1 with the yield of 80%. HRMS (C) 24 H 16 BrN):m/z 397.0412。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine-substituted compound 2-1, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 100 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bipolar main material 2-2 with yield of 78%. HRMS (C) 45 H 30 N 4 ):m/z 627.2613。
The bipolar host material 2-2 prepared in this example was used as a host material, and Ir (tptptpy) 2 The acac is an OLED device prepared from the guest luminescent material, and the device structure is as follows: ITO/HATCN (5nm)/TAPC (50nm)/TcTa (5nm)/3 wt% Ir (tptppy) 2 acac 2-2(20nm)/TmPyPB (40nm)/LiF (1nm)/Al, and the device performance is tested.
The luminance-voltage-current density test results are shown in FIG. 3, and from FIG. 3, the maximum luminance of the OLED device prepared by using the host material of this embodiment can be 145900cd/m 2 The starting voltage is as low as 2.5V.
Fig. 4 is an electroluminescence spectrum of an OLED device prepared using the bipolar host material of the present example.
Example 8
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000171
mixing 15mmol of (4- (3, 6-di-tert-butyl-9 hydro-carbazol-9-yl) phenyl) boric acid, 13.6mmol of p-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of a mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 95 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 2-3 with the yield of 75%. HRMS (C) 32 H 32 BrN):m/z 509.1785。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 2-3, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 95 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bipolar main material 2-4 with the yield of 79%. HRMS (C) 53 H 46 N 4 ):m/z 738.3821。
Example 9
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000172
mixing 15mmol of 4-triphenylamine borate, 13.6mmol of p-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 90 deg.C for 8 hr, and using after reactionExtracting with dichloromethane and water, concentrating, and separating and purifying with silica gel column chromatography to obtain bromine substituted compound 2-5 with yield of 66%. HRMS (C) 24 H 18 BrN):m/z399.0672。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 2-5, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 90 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bipolar main material 2-6 with yield of 81%. HRMS (C) 45 H 32 N 4 ):m/z 628.2689。
Example 10
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000181
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of 2-iodo-5-bromobiphenyl, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, evacuating gas in a reaction flask for three times, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 110 ℃ for reaction for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 2-7 with the yield of 72%. HRMS (C) 30 H 20 BrN):m/z 473.0842。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 2-7, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 110 deg.C for 8 hr, extracting with dichloromethane and water, concentrating, and separating and purifying by silica gel column chromatographyTo obtain the bipolar host material 2-8 with a yield of 60%. HRMS (C) 51 H 34 N 4 ):m/z 702.8798。
Example 11
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000191
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of p-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 120 ℃ for reaction for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 2-1 with the yield of 80%. HRMS (C) 24 H 16 BrN):m/z 397.0412。
15mmol of (4- (4, 6-diphenylpyrimidin-2-yl) phenyl) boronic acid, 13.6mmol of a bromine-substituted compound 2-1, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium were mixed, and a gas was evacuated three times in a reaction flask, and then 50mL of a mixed solvent in which the volume ratio of toluene, ethanol and water was 8: 1: 1. heating and refluxing at 120 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bipolar main material 2-9 with yield of 72%. HRMS (C) 46 H 31 N 3 ):m/z 625.7788。
Example 12
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000201
15mmol of boron- [4- (3, 6-diphenyl-9-hydro-carbazol-9-yl) phenyl]Boric acid, 13.6mmol of p-bromoiodobenzene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium were mixed, and the gas was purged three times in a reaction flask, thenThen 50mL of mixed solvent is added, and the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 115 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bromine substituted compound 2-10 with yield of 76%. HRMS (C) 24 H 16 BrN):m/z 549.1077。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 2-10, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 115 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bipolar host material 2-11 with yield of 67%. HRMS (C) 57 H 38 N 4 ):m/z 778.3012。
Example 13
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000211
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of 1, 8-dibromonaphthalene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing for three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 100 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain a bromine substituted compound 3-1 with the yield of 54%, wherein the nuclear magnetic resonance spectrum analysis comprises the following steps: 1 H NMR(500MHz,CDCl 3 ,δ)8.18(d,J＝7.7,2H),7.96–7.93(m,2H),7.87–7.85(m,1H),7.60–7.52(m,8H),7.48–7.45(m,2H),7.39–7.30(m,3H)。HRMS(C 28 H 18 BrN):m/z 447.0601。
15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine and 13.6mmol of bromine are substitutedMixing the compound 3-1, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing for three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 100 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bipolar main body material 3-2 with the yield of 61%, wherein the nuclear magnetic resonance spectrum analysis comprises the following steps: 1 H NMR(500MHz,CDCl 3 ,δ)8.72–8.70(m,4H),8.57–8.55(m,2H),8.06(dt,J＝8.1,1.6Hz,2H),7.88–7.87(m,2H),7.70–7.54(m,10H),7.37–7.33(m,4H),7.22(m,2H),7.16–7.06(m,2H),7.04–6.86(m,4H)。HRMS(C 49 H 32 N 4 ):m/z 677.2706。
the bipolar host material 3-2 prepared in this example was used as a host material, and Ir (tptppy) 2 The acac is an OLED device prepared from the guest luminescent material, and the device structure is as follows: ITO/HATCN (5nm)/TAPC (50nm)/TcTa (5nm)/3 wt% Ir (tptppy) 2 acac 3-2(20nm)/TmPyPB (40nm)/LiF (1nm)/Al, and the device performance is tested.
The luminance-voltage-current density test results are shown in FIG. 5, and from FIG. 5, the maximum luminance of the OLED device prepared by using the bipolar host material of this embodiment can be 97620cd/m 2 The starting voltage is as low as 3.7V.
Fig. 6 is an electroluminescence spectrum of an OLED device prepared using the bipolar host material of the present example.
Example 14
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000221
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of 1, 8-dibromonaphthalene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 110 deg.C for 8h, and using dichloromethane after reactionExtracting with alkane and water, concentrating, and separating and purifying with silica gel column chromatography to obtain bromine substituted compound 3-3 with yield of 62%. HRMS (C) 36 H 34 BrN):m/z 559.1798。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 3-3, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 110 deg.C for 8 hr, extracting with dichloromethane and water, concentrating, and separating and purifying with silica gel column chromatography to obtain main material 3-4 with yield of 59%. HRMS (C) 57 H 48 N 4 ):m/z 788.3925。
Example 15
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000231
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of 1, 8-dibromonaphthalene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 95 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain 3-5 bromine substituted compounds with the yield of 67%. HRMS (C) 28 H 20 BrN):m/z 449.0710。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 3-5, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 95 deg.C for 8 hr, extracting with dichloromethane and water, concentrating, and separating and purifying by silica gel column chromatography to obtain bipolar main material3-6, yield 72%. HRMS (C) 49 H 34 N 4 ):m/z 678.2751。
Example 16
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000241
15mmol of [4- (9-hydro-carbazol-9-yl) -3-methylphenyl]Mixing boric acid, 13.6mmol of 1, 8-dibromonaphthalene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 120 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 3-7 with the yield of 64%. HRMS (C) 29 H 20 BrN):m/z 449.0710。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) group-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 3-7, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 120 deg.C for 8 hr, extracting with dichloromethane and water, concentrating, and separating and purifying by silica gel column chromatography to obtain bipolar main material 3-8 with yield of 71%. HRMS (C) 50 H 34 N 4 ):m/z 690.2742。
Example 17
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000251
mixing 15mmol of 4- (9H-carbazol-9-yl) phenylboronic acid, 13.6mmol of 1, 8-dibromonaphthalene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, evacuating the reaction flask for three times, and adding 50mL of mixed solutionAnd (3) mixing the solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 115 ℃ for 8h, extracting with dichloromethane and water after the reaction is finished, concentrating, and separating and purifying by silica gel column chromatography to obtain the bromine substituted compound 3-1 with the yield of 56%. HRMS (C) 28 H 18 BrN):m/z 447.0601。
15mmol of (4- (4, 6-diphenylpyrimidin-2-yl) phenyl) boronic acid, 13.6mmol of the bromine-substituted compound 3-1, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium were mixed, and a gas was evacuated three times in a reaction flask, and then 50mL of a mixed solvent in which the volume ratio of toluene, ethanol and water was 8: 1: 1. heating and refluxing at 115 deg.C for 8 hr, extracting with dichloromethane and water, concentrating, and separating and purifying by silica gel column chromatography to obtain bipolar main material 3-9 with yield of 65%. HRMS (C) 50 H 33 N 3 ):m/z 675.2612。
Example 18
The synthesis procedure of this example is as follows:
Figure BDA0003707821420000261
15mmol of boron- [4- (3, 6-diphenyl-9-hydro-carbazol-9-yl) phenyl]Mixing boric acid, 13.6mmol of 1, 8-dibromonaphthalene, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is 8: 1: 1. heating and refluxing at 120 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bromine substituted compound 3-10 with a yield of 52%. HRMS (C) 40 H 26 BrN):m/z 599.1197。
Mixing 15mmol of 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) base-1, 3, 5-triazine, 13.6mmol of bromine substituted compound 3-10, 40.9mmol of potassium carbonate and 0.41mmol of tetrakis (triphenylphosphine) palladium, vacuumizing three times in a reaction bottle, and adding 50mL of mixed solvent, wherein the volume ratio of toluene, ethanol and water in the mixed solventIs 8: 1: 1. heating and refluxing at 120 deg.C for 8h, extracting with dichloromethane and water after reaction, concentrating, and separating and purifying with silica gel column chromatography to obtain bipolar main material 3-11 with yield of 66%. HRMS (C) 61 H 40 N 4 ):m/z 828.3212。
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A bipolar host material having one of the structures represented by the following formulae 1-3:
Figure FDA0003707821410000011
wherein Ar is 1 Independently an electron-donating aromatic ring derivative group, Ar 2 Independently an electron-withdrawing aromatic ring derivative group;
R 1 、R 2 、R 3 、R 4 、R 5 and R 6 Independently hydrogen, methyl or phenyl.
2. A method of making a bipolar host material as defined in claim 1, comprising the steps of:
s1, mixing halogenated hydrocarbon, an electron-donating aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and a mixed solvent, and then carrying out substitution reaction to obtain a bromine substituted compound;
s2, mixing a bromine substituted compound, an electron-withdrawing aromatic boric acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium and a mixed solvent, and then carrying out substitution reaction to obtain a bipolar main body material;
the halogenated hydrocarbon is bromoiodobenzene, bromoiodobiphenyl or dibrombinaphthyl.
3. The method according to claim 2, wherein the temperature of the substitution reaction in step S1 and step S2 is 90 to 120 ℃ independently, and the time is 6 to 24 hours independently.
4. The preparation method of claim 3, wherein the mixed solvent in the steps S1 and S2 is a mixture of toluene, ethanol and water, and the volume ratio of toluene, ethanol and water is 2-9: 1: 1 to 2.
5. The production method according to claim 2 or 4, wherein the electron-donating aromatic boronic acid derivative is one of 4- (9-hydro-carbazol-9-yl) phenylboronic acid, (4- (3, 6-di-tert-butyl-9-hydro-carbazol-9-yl) phenyl) boronic acid, triphenylamine-4-borate, and boron- [4- (3, 6-diphenyl-9-hydro-carbazol-9-yl) phenyl ] boronic acid.
6. The production method according to claim 3 or 4, wherein the electron-withdrawing aromatic boronic acid derivative is 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) yl-1, 3, 5-triazine or (4- (4, 6-diphenylpyrimidin-2-yl) phenyl) boronic acid.
7. The production method according to claim 5, wherein the molar volume ratio of the halogenated hydrocarbon, the electron-donating aromatic boronic acid derivative, the potassium carbonate, the tetrakis (triphenylphosphine) palladium, and the mixed solvent is 1 mmol: 1-4 mmol: 3-5 mmol: 0.02-0.05 mmol: 2.5-5 mL.
8. The production method according to claim 2, 3, 4 or 7, wherein the molar volume ratio of the bromine-substituted compound, the electron-withdrawing aromatic boronic acid derivative, potassium carbonate, tetrakis (triphenylphosphine) palladium, and the mixed solvent is 1 mmol: 1-4 mmol: 3-5 mmol: 0.02-0.05 mmol: 2.5-5 mL.
9. Use of the bipolar host material of claim 1 in an organic electroluminescent diode.
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