CN109206422B - Bipolar compound based on 1,3, 4-thiadiazole and preparation method and application thereof - Google Patents

Bipolar compound based on 1,3, 4-thiadiazole and preparation method and application thereof Download PDF

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CN109206422B
CN109206422B CN201811131512.6A CN201811131512A CN109206422B CN 109206422 B CN109206422 B CN 109206422B CN 201811131512 A CN201811131512 A CN 201811131512A CN 109206422 B CN109206422 B CN 109206422B
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thiadiazole
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穆广园
庄少卿
任春婷
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Hubei Shang Shang photoelectric material Co., Ltd.
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Hubei Sunshine Optoelectronics Material Co ltd
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Abstract

The invention takes 1,3, 4-thiadiazole with strong electron-withdrawing ability as a core group, and the 2 and 5 positions of the thiadiazole respectively take arylene as a pi bridge to be connected with a group with electron-donating/acceptor ability, thereby forming a novel bipolar compound. The 1,3, 4-thiadiazole is an ideal light-emitting layer material, and the symmetric strong electron-pulling capability of a parent nucleus structure enables a compound extending through a pi bridge to present an ordered close-packed structure, and the compound has a certain rigidity given by a bipolar benzo heterocyclic ring, so that low optical loss caused by light near a cathode can be realized, and the light extraction efficiency is improved. Meanwhile, the compound has a parent nucleus of strong electron pulling and a donor/acceptor group, so that the compound has strong charge balance capability, the conjugation interrupted by the pi bridge effectively solves the problem of band gap reduction caused by charge transfer in the electron donor group and the electron withdrawing group, and the compound is an excellent luminescent layer main body material with lower driving voltage, higher device efficiency and smaller efficiency slip.

Description

Bipolar compound based on 1,3, 4-thiadiazole and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photoelectric material application, and particularly relates to a bipolar compound based on 1,3, 4-thiadiazole and a preparation method and application thereof.
Background
OLEDs, i.e. organic light emitting diodes, are also known as organic electroluminescent displays (OLEDs). The OLED has a self-luminous characteristic, adopts a very thin organic material coating layer and a glass substrate, emits light when current passes through the organic material coating layer, has a large viewing angle of an OLED display screen, and can significantly save electricity, so the OLED is regarded as one of the most promising products in the 21 st century.
There are three main classes of organic electroluminescent materials: small molecule organic compounds, polymers, and oligomers. Small molecule organic compounds and polymers are the most widely used organic electroluminescent materials at present, the polymer materials are generally used for preparing organic electroluminescent devices through dissolution spin coating, the rigid conjugated system has the majority of poor main chain solubility, the energy level difference between HOMO and LUMO is narrow, and small molecule series materials are often used for preparing the organic electroluminescent devices due to simple synthesis process and good energy level matching degree.
Most organic small molecule semiconductor materials are biased to transmit a certain carrier (electron or hole) due to chemical structure and energy level characteristics, while the transmission capability of the other corresponding carrier is low, and organic small molecule bipolar materials become research hotspots in recent years due to the functions of balancing the concentration of the electron and the hole in the device, simplifying the device structure, controlling an exciton recombination region and the like, so as to improve the efficiency and the stability of the organic electroluminescent device.
In addition, the organic electroluminescent device is a multilayer sandwich type double-carrier direct current injection device, so that the structure of the device has important influence on various performances of the device, such as driving voltage, luminous efficiency, device service life and the like. The common structure of the organic electroluminescent device is an anode, a single-layer or multi-layer organic functional film and a cathode, and because the refractive index difference between the cathode and cover plate glass is large, the light of the OLED can generate strong reflection loss through the cathode, so how to reduce the internal dissipation of the light in the device and improve the light extraction efficiency through the structural design is the problem to be solved in the field of the OLED.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a novel 1,3, 4-thiadiazole-based nonpolar compound, which is applied to an organic light emitting device to improve the efficiency and stability of the organic light emitting device, solve the problem of internal loss of light in the organic light emitting device, and improve the light extraction efficiency thereof.
The invention provides a bipolar compound based on 1,3, 4-thiadiazole, which has a structural general formula as shown in the following (I):
Figure BDA0001813665380000021
wherein Ar is1、Ar2Independently are: any one of substituted or unsubstituted arylene groups having 6 to 24 carbon atoms, Ar1、Ar2The same or different;
R1、R2、R3、R4、R5、R6、R7、R8independently are: any one of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted or unsubstituted heterocyclic group having 5 to 12 carbon atoms, R1、R2、R3、R4、R5、R6、R7、R8The same or different;
X1、X2independently are: s, O-S-O, O or N-L;
wherein L is selected from: any one of a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 6 to 24 carbon atoms, a substituted or unsubstituted fluorenyl group having 12 to 24 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 24 carbon atoms, X1、X2The same or different.
When X is present, X is1、X2Independently are: when O ═ S ═ O or N-L, the substitution sites are on either S or N.
As a preferred technical scheme of the invention, when Ar is used1、Ar2Independently are: when any one of the substituted arylene groups having a carbon number of 6 to 24 is substituted, the substituent of the arylene group is selected from: alkyl group having 1 to 4 carbon atoms, aryl group having 6 to 10 carbon atomsAny one of (1);
when said R is1、R2、R3、R4、R5、R6、R7、R8Independently are: when any one of a substituted aryloxy group having 6 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms, and a substituted heterocyclic group having 5 to 12 carbon atoms is used, the substituents for the aryloxy group, the aryl group, and the heterocyclic group are each independently selected from the group consisting of: any one of an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 10 carbon atoms;
when said L is selected from: when any one of a substituted aryl group having 6 to 24 carbon atoms, a substituted aromatic heterocyclic group having 6 to 24 carbon atoms, a substituted fluorenyl group having 12 to 24 carbon atoms, and a substituted arylamine group having 6 to 24 carbon atoms is used, the substituents for the aryl group, the aromatic heterocyclic group, the fluorenyl group, and the arylamine group are each independently selected from the group consisting of: an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
As a preferable technical means of the present invention, R is1、R2、R3、R4、R5、R6、 R7、R8All hydrogen, the structural general formula of the bipolar compound is shown as the following (II):
Figure BDA0001813665380000031
as a preferable embodiment of the present invention, Ar is1、Ar2Each independently selected from: any one of phenylene group unsubstituted, substituted with alkyl group having carbon number of 1 to 4 or substituted with aryl group having carbon number of 6 to 10, any one of biphenylene group unsubstituted, substituted with alkyl group having carbon number of 1 to 4 or substituted with aryl group having carbon number of 6 to 10, or any one of naphthylene group unsubstituted, substituted with alkyl group having carbon number of 1 to 4 or substituted with aryl group having carbon number of 6 to 10.
As a preferable embodiment of the present invention, X is1、X2Are respectively N-L, wherein, the X is1、X2The corresponding L is independently selected from: any one of an aryl group having a carbon number of 6 to 24 which is unsubstituted, substituted with an alkyl group having a carbon number of 1 to 4 or substituted with an aryl group having a carbon number of 6 to 10, any one of an aromatic heterocyclic group having a carbon number of 6 to 24 which is unsubstituted, substituted with an alkyl group having a carbon number of 1 to 4 or substituted with an aryl group having a carbon number of 6 to 10, or any one of a fluorenyl group having a carbon number of 12 to 24 which is unsubstituted or substituted with an aryl group having a carbon number of 6 to 10.
As a preferable embodiment of the present invention, X is1、X2Each independently selected from any one of the following structures:
Figure BDA0001813665380000041
specific examples of the 1,3, 4-thiadiazole-based bipolar compound of the present embodiment represented by the general formula (I) include 1,3, 4-thiadiazole-based bipolar compounds having the structures represented by the compounds (1) to (193). However, the present invention is not limited thereto.
Figure BDA0001813665380000042
Figure BDA0001813665380000051
Figure BDA0001813665380000061
Figure BDA0001813665380000071
Figure BDA0001813665380000081
Figure BDA0001813665380000091
Figure BDA0001813665380000101
Figure BDA0001813665380000111
Figure BDA0001813665380000121
In a second aspect, the present invention provides a process for the preparation of 1,3, 4-thiadiazole based bipolar compounds, comprising the following scheme:
Figure BDA0001813665380000122
the synthesis steps are as follows:
s1, intermediate A10、Ar1Feeding the corresponding substituted halogenated boric acid derivative and potassium carbonate according to the molar ratio of 1 (1-3) to 2-4, and adding the intermediate A10: toluene: ethanol: water 1 mmol: 1-4 mL: 1-4 mL: adding 1-4mL of toluene, ethanol and water, and adding the intermediate A under the protection of nitrogen10Adding 1 per mill-5% of tetrakis (triphenylphosphine) palladium, heating to 60-100 deg.C, reacting for 6-30h to obtain intermediate A1；
Intermediate A20、Ar2Feeding the corresponding substituted halogenated boric acid derivative and potassium carbonate according to the molar ratio of 1 (1-3) to 2-4, and adding the intermediate A20: toluene: ethanol: water 1 mmol: 1-4 mL: 1-4 mL: adding 1-4mL of toluene, ethanol and water, and adding the intermediate A under the protection of nitrogen20Adding 1 per mill-5% of palladium tetrakis (triphenylphosphine) into the mixture, heating the mixture to 60-100 ℃, and reactingReacting for 6-30h to obtain an intermediate A2；
S2, intermediate A according to1: tetrahydrofuran was 1 mmol: 2-5mL of the intermediate A1Dissolving in tetrahydrofuran, cooling to-78 deg.C under nitrogen protection, stirring for 0.3-2h, mixing with n-butyllithium cyclohexane solution1The ratio is 0.2-4mL: after 1mmol addition and reaction for 0.5-3h, as described for intermediate A1Adding 1-3 times of triethyl borate, continuing to react for 1-4h, heating to room temperature, reacting for 6-20h, cooling to 0 ℃, and adding the intermediate A1: hydrochloric acid 1 mmol: 0.2-4mL of hydrochloric acid solution is added for hydrolysis reaction, and an intermediate B is obtained after treatment1；
According to said intermediate A2: tetrahydrofuran was 1 mmol: 2-5mL of the intermediate A2Dissolving in tetrahydrofuran, cooling to-78 deg.C under nitrogen protection, stirring for 0.3-2h, mixing with n-butyl lithium cyclohexane solution2Adding 1mmol of the intermediate A according to the proportion of 0.2-4mL and reacting for 0.5-3h1Adding 1-3 times of triethyl borate, continuing to react for 1-4h, heating to room temperature, reacting for 6-20h, cooling to 0 ℃, and adding the intermediate A1: hydrochloric acid 1 mmol: 0.2-4mL of hydrochloric acid solution is added for hydrolysis reaction, and an intermediate B is obtained after treatment1；
S3 and the intermediate B1Feeding 2-bromo-5-chloro-1, 3, 4-thiadiazole and potassium carbonate according to the molar ratio of 1 (1-3) to 2-4, and adding the intermediate B1: toluene: ethanol: water 1 mmol: 1-10 mL: 1-10 mL: adding 1-10mL of toluene, ethanol and water, and adding the intermediate B under the protection of nitrogen1Adding 1 per mill-5% of tetrakis (triphenylphosphine) palladium, heating to 60-100 deg.C, reacting for 4-30h, returning to room temperature, and adding into intermediate B1In an amount of 1 to 3 times the amount of the intermediate B2Heating to 60-100 ℃ for reaction for 6-30h, and processing to obtain the target compound C after the reaction is finished.
A third aspect of the present invention provides an organic light-emitting element comprising: the light-emitting layer is made of the bipolar compound based on 1,3, 4-thiadiazole, and is laminated on the cathode, and the cathode is laminated on the anode.
As a preferable technical solution, the organic light emitting element further includes a light emitting layer, the light emitting layer is sandwiched between the anode and the cathode, and a material of the light emitting layer includes the bipolar compound based on 1,3, 4-thiadiazole as described above.
The invention takes 1,3, 4-thiadiazole with strong electron-withdrawing ability as a core group, and the 2 and 5 positions of the thiadiazole respectively take arylene as a pi bridge to be connected with a group with electron-donating/acceptor ability, thereby forming a novel bipolar compound. The symmetric strong electron pulling capability of the parent-nucleus structure of the 1,3, 4-thiadiazole enables the compound structure extending through a pi bridge to present an ordered close-packed structure, the introduction of the bipolar benzo heterocyclic ring further increases the rigidity and the steric hindrance of the whole structure of the compound, the compound is added outside an electrode as a light emitting layer, the low optical loss caused by light near a cathode can be realized, the light extraction efficiency is improved, and the compound is an ideal light emitting layer material. In addition, the compound has a strong electron-pulling mother nucleus structure and an electron-donating/acceptor group, so that the compound has strong charge balance capability, the conjugation interrupted by the pi bridge effectively improves the problem of band gap reduction caused by the charge of electron-donating and electron-withdrawing groups in one molecule through the charge in the molecule, when the compound is used as a light-emitting layer host material to be applied to an organic electroluminescent device, the higher triplet state energy level and the wider band gap of the compound can effectively prevent reverse energy transfer from an object to the host, the balanced charge transfer capability ensures the composite transition of carriers in a light-emitting layer to a greater extent, the device is endowed with lower driving voltage, higher device efficiency and smaller efficiency slip, and the compound is also an excellent light-emitting layer host material.
Drawings
FIG. 1 is a schematic structural view of an organic electroluminescent device having a light emitting layer structure according to the present invention;
FIG. 2 is a graph of wavelength versus light intensity characteristics for device 4, device 14, and device 26;
fig. 3 is a graph of the voltage-current density-luminance characteristics of device 4, device 14, and device 26;
FIG. 4 is a graph of current density-current efficiency-power efficiency characteristics for device 4, device 14, and device 26;
fig. 5 is a graph of luminance versus external quantum efficiency characteristics of device 4, device 14, and device 26.
Detailed Description
The present invention will be further described with reference to the following examples. Any simple modifications, equivalent changes and the like of the following embodiments according to the technical essence of the present invention still fall within the protection scope of the technical solution of the present invention. The present invention is not limited to the contents described in the following embodiments.
Example 1: the compound (1) can be synthesized by the following method:
Figure BDA0001813665380000151
(1) synthesis of intermediate a:
2-bromo-1H-benzimidazole (39.41g,200mmol), iodobenzene (40.79g,200mmol), crown ether (5.29g,20mmol), potassium carbonate (82.92g,600mmol), and dimethylacetamide (200g) were added to a 500mL three-necked flask, and under nitrogen protection, cuprous iodide (3.81g,20mmol) was added, the temperature was raised to 165 ℃ for 12H, and the reaction was stopped by HPLC monitoring the completion of the reaction and lowering the temperature. Washing with water, filtering, pulping with ethanol once to obtain intermediate a0: 47.52g of 2-bromo-1-phenyl-1H-benzimidazole was obtained, yield 87%.
In a 1L three-necked flask, the intermediate a is added0(40.97g,150mmol), 4-bromobenzeneboronic acid (30.12g,150mmol), potassium carbonate (41.46g,300mmol), toluene (300mL), ethanol (150mL), water (150mL), under nitrogen protection, tetrakis (triphenylphosphine) palladium (0.35g,0.3mmol) was added continuously, the temperature was raised to 85 ℃ for reaction for 10h, HPLC was used to monitor the completion of the reaction, and the reaction was stopped by cooling. Washing, filtering, concentrating mother liquor, combining filter residue and concentrated mother liquor, and separating by column chromatography to obtain an intermediate a: 2- (4-bromophenyl) -1-phenyl-1H-benzene44.00g of benzimidazole in 84% yield.
(2) Synthesis of intermediate b:
adding the intermediate a (34.92g,100mmol) and tetrahydrofuran (350mL) into a 1L three-necked bottle, cooling to-78 ℃ under the protection of nitrogen, stirring for 0.5h, slowly adding a 2mol/L n-butyl lithium cyclohexane solution 50mL by using a dropping funnel, reacting for 1h, then adding triethyl borate (14.60g, 100mmol), continuing to react for 2h, heating to room temperature, reacting for 10h, monitoring by HPLC to complete the reaction, cooling to 0 ℃, adding 100mL of 2mol/L hydrochloric acid to perform hydrolysis reaction, standing for liquid separation, extracting an aqueous layer twice by using ethyl acetate, combining organic layers, and concentrating to obtain an intermediate b: 25.13g of (4- (1-phenyl-1H-benzimidazol-2-yl) phenyl) boronic acid was obtained in a yield of 80%.
(3) Synthesis of target compound c:
adding the intermediate b (21.99g,70mmol), 2-bromo-5-chloro-1, 3, 4-thiadiazole (6.98g, 35mmol), potassium carbonate (19.35g,140mmol), toluene (150mL), ethanol (70mL) and water (70mL) into a 500mL three-necked flask, continuously adding tetrakis (triphenylphosphine) palladium (0.16g,0.14mmol) under the protection of nitrogen, heating to 85 ℃, reacting for 14h, monitoring by HPLC (high performance liquid chromatography), and cooling to stop the reaction. Washing, filtering, concentrating the mother liquor, combining filter residue and the concentrated mother liquor, and separating by column chromatography to obtain a target compound c: 19.18g of the compound (1) was obtained in 88% yield.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 622.7496, theoretical molecular weight: 622.7500, respectively; call for C40H26N6(%) C77.15, H4.21, N13.50 Found C77.15, H4.20, N13.50. From the mass spectrum data and the results of elemental analysis, the product was found to have a correct structure and to be the compound (1).
Example 2: compound (20) can be synthesized by the following method:
Figure BDA0001813665380000161
(1) intermediate a1、a2The synthesis of (2):
replacement of iodobenzene (40.79g,200mmol) in example 1(1) with 2-iododibenzoFuran (58.82g,200mmol), the other synthesis was the same as example 1 intermediate a0The synthesis process of (1) to obtain an intermediate a10: 60.29g of 2-bromo-1- (dibenzofuran-2-yl) -1H-benzimidazole, yield 83%;
a in example 1(1)0(40.97g,150mmol) was replaced with a in this example10(54.48g, 150mmol), the other synthetic process was the same as that of intermediate a in example 1, to obtain intermediate a1: 52.72g of 2- (4-bromophenyl) -1- (dibenzofuran-2-yl) -1H-benzimidazole, yield 80%;
the iodobenzene (40.79g,200mmol) in example 1(1) was replaced by 3-iodo-1, 1' -biphenyl (56.02g,200mmol), and the synthesis was otherwise identical to example 1, intermediate a0The synthesis process of (1) to obtain an intermediate a20: 1- ([1,1' -Biphenyl)]59.37g of (E) -3-yl) -2-bromo-1H-benzimidazole, yield 85%;
a in example 1(1)0(40.97g,150mmol) was replaced with a in this example20(52.38g, 150mmol), the other synthetic process was the same as that of intermediate a in example 1, to obtain intermediate a2: 53.59g of 2- (4-bromophenyl) -1- (dibenzofuran-2-yl) -1H-benzimidazole, yield 84%.
(2) Intermediate b1、b2The synthesis of (2):
the a (34.92g,100mmol) in example 1(2) was replaced by a in this example1(43.93g, 100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to give intermediate b1: 32.34g of (4- (1- (dibenzofuran-2-yl) -1H-benzimidazol-2-yl) phenyl) boronic acid was obtained in a yield of 80%.
The a (34.92g,100mmol) in example 1(2) was replaced by a in this example2(42.53g, 100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b2: (4- (1- ([1,1' -Biphenyl)]-3-yl) -1H-benzimidazol-2-yl) phenyl) boronic acid 31.22g, yield 80%.
(3) Synthesis of target compound c:
in a 500mL three-necked flask, intermediate b was added1(14.15g,35mmol), 2-bromo-5-chloro-1, 3, 4-thiadiazole (6.98g, 35mmol), potassium carbonate (19.35g,140mmol), toluene (150mL), ethanol (70mL), water (70mL), under the protection of nitrogen, adding tetrakis (triphenylphosphine) palladium (0.16g,0.14mmol) continuously, heating to 85 ℃, reacting for 7h, monitoring the reaction completion by HPLC, returning to room temperature, adding intermediate b2(13.66g,35mmol) and continued reaction for 10h, HPLC monitored completion and the reaction stopped by cooling. Washing, filtering, concentrating the mother liquor, combining filter residue and the concentrated mother liquor, and separating by using column chromatography to obtain a target compound c: 19.88g of the compound (20) was obtained in a yield of 72%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 788.9296, theoretical molecular weight: 788.9290, respectively; call for C52H32N6(%) C79.17, H4.09, N10.65 Found C79.18, H4.10, N10.65. From the mass spectrum data and the results of elemental analysis, the product was found to be a correct structure and to be compound (20).
Example 3: compound (35) can be synthesized by the following method:
Figure RE-GDA0001885116540000171
(1) intermediate a0The synthesis of (2):
the iodobenzene (40.79g,200mmol) in example 1(1) was replaced by 2-iodonaphthalene (50.81g,200mmol), and the synthesis was otherwise identical to that of intermediate a in example 10The synthesis process of (1) to obtain an intermediate a0: 54.30g of 2-bromo-1- (naphthalen-2-yl) -1H-benzimidazole, 84% yield;
a in example 1(1)0(40.97g,150mmol) was replaced with a in this example0(48.48g, 150mmol), the other synthesis was the same as that of intermediate a in example 1, to obtain intermediate a: 2- (4-bromophenyl) -1- (naphthalen-2-yl) -1H-benzimidazole 49.11g, yield 82%; (2) Synthesis of intermediate b:
intermediate b was obtained by substituting a (34.92g,100mmol) in example 1(2) with a (39.93g, 100mmol) in this example and the other synthesis procedures were the same as those for intermediate b in example 1: 29.50g of (4- (1- (naphthalen-2-yl) -1H-benzimidazol-2-yl) phenyl) boronic acid was obtained in a yield of 81%.
(3) Synthesis of intermediate c:
the synthesis of the target compound c in example 1 was carried out in the same manner as in example 1 except that b (21.99g,70mmol) in example 1(3) was replaced with b (25.49g, 70mmol) in this example, whereby the target compound c: 21.51g of Compound (35), yield 85%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 722.8695, theoretical molecular weight: 722.8700, respectively; call for C48H30N6(%) C79.76, H4.18, N11.63 Found C79.75, H4.20, N11.62. From the mass spectrum data and the results of elemental analysis, the product was found to be a correct structure, compound (35).
Example 4: compound (69) can be synthesized by the following method:
Figure BDA0001813665380000181
(1) intermediate a1、a2The synthesis of (2):
the iodobenzene (40.79g,200mmol) in example 1(1) was replaced with 4-iodo-9, 9-dimethyl-9H-fluorene (63.83g,200mmol), and the synthesis procedure was otherwise the same as for intermediate a in example 10The synthesis process of (1) to obtain an intermediate a10: 2-bromo-1- (9, 9-dimethyl-9H-fluoren-4-yl) -1H-benzimidazole 63.84g, yield 82%;
a in example 1(1)0(40.97g,150mmol) was replaced with a in this example10(58.39g, 150mmol), 4-bromobenzeneboronic acid (30.12g,150mmol) was replaced by 3-bromobenzeneboronic acid (30.12g,150mmol), and the other synthetic procedures were the same as those of intermediate a in example 1, to obtain intermediate a1: 54.45g of 2- (3-bromophenyl) -1- (9, 9-dimethyl-9H-fluoren-4-yl) -1H-benzimidazole in 78% yield;
the intermediate a can be obtained by replacing 4-bromobenzeneboronic acid (30.12g,150mmol) in example 1(1) with 3-bromobenzeneboronic acid (30.12g,150mmol) and performing the same synthetic process as the intermediate a in example 12: 2- (3-bromophenyl) -1-phenyl-1H-Benzimidazole 44.00g, yield 84%.
(2) Intermediate b1、b2The synthesis of (2):
the a (34.92g,100mmol) in example 1(2) was replaced by a in this example1(46.54g, 100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b1: 33.99g of (3- (1- (9, 9-dimethyl-9H-fluoren-4-yl) -1H-benzimidazol-2-yl) phenyl) boronic acid was obtained in a yield of 79%.
The a (34.92g,100mmol) in example 1(2) was replaced by a in this example2(34.92g,100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b2: 25.44g of (3- (1-phenyl-1H-benzimidazol-2-yl) phenyl) boronic acid was obtained in a yield of 81%.
(3) Synthesis of target compound c:
b in example 2(3)1(14.15g,35mmol) was replaced with b in this example1(15.06g,35mmol) of b in example 2(3)2(13.66g,35mmol) was replaced with b in this example2(11.00g,35mmol), and the other synthesis procedures were the same as those of the objective compound c of example 2, to obtain the objective compound c: 19.40g of the compound (69) was obtained in a yield of 75%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 738.9136, theoretical molecular weight: 738.9130, respectively; call for C49H34N6(%) C79.65, H4.64, N11.37 Found C79.65, H4.65, N11.35. From the mass spectrum data and the elemental analysis results, the product was correct in structure and was a compound (69).
Example 5: compound (96) can be synthesized by the following method:
Figure BDA0001813665380000191
(1) intermediate a1、a2The synthesis of (2):
the 4-bromobenzeneboronic acid (30.12g,150mmol) in example 1(1) was replaced with 3-bromobenzeneboronic acid (30.12g,150mmol), and the other syntheses were carried out in the same manner as aboveExample 1 Synthesis of intermediate a1: 44.00g of 2- (3-bromophenyl) -1-phenyl-1H-benzimidazole was obtained in 84% yield.
The iodobenzene (40.79g,200mmol) in example 1(1) was replaced by 3-iodo-9-phenyl-9H-carbazole (73.84g,200mmol), and the synthesis was otherwise identical to that of intermediate a in example 10The synthesis process of (1) to obtain an intermediate a20: 70.13g of 3- (2-bromo-1H-benzimidazole-1-yl) -9-phenyl-9H-carbazole, wherein the yield is 80%;
a in example 1(1)0(40.97g,150mmol) was replaced with a in this example20(65.75g, 150mmol), 4-bromobenzeneboronic acid (30.12g,150mmol) was replaced with 3-bromobenzeneboronic acid (30.12g,150mmol), and the other synthetic procedures were the same as those of intermediate a in example 1, to obtain intermediate a2: 59.42g of 3- (2- (3-bromophenyl) -1H-benzimidazol-1-yl) -9-phenyl-9H-carbazole, yield 77%;
(2) intermediate b1、b2The synthesis of (2):
the a (34.92g,100mmol) in example 1(2) was replaced by a in this example1(34.92g,100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b1: 25.44g of (3- (1-phenyl-1H-benzimidazol-2-yl) phenyl) boronic acid was obtained in a yield of 81%.
The a (34.92g,100mmol) in example 1(2) was replaced by a in this example2(51.44g, 100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b2: 38.34g of (3- (1- (9-phenyl-9H-carbazol-3-yl) -1H-benzimidazol-2-yl) phenyl) boronic acid (yield 80%).
(3) Synthesis of target compound c:
b in example 2(3)1(14.15g,35mmol) was replaced with b in this example1(11.00g,35mmol) of b in example 2(3)2(13.66g,35mmol) was replaced with b in this example2(16.78g,35mmol), and the other synthesis procedures were the same as those of the objective compound c of example 2, to obtain the objective compound c: compound (96)20.40g, yield 74%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 787.9443, theoretical molecular weight: 787.9450, respectively; call for C52H33N7(%) C79.27, H4.22, N12.44 Found C79.25, H4.22, N12.45. From the mass spectrometry data and the results of elemental analysis, the product was correct in structure and was a compound (96).
Example 6: compound (121) can be synthesized by the following method:
Figure BDA0001813665380000211
(1) synthesis of intermediate a:
the procedure of example 1 was otherwise the same as that for intermediate a, except that 4-bromobenzeneboronic acid (30.12g,150mmol) in example 1(1) was replaced with (3 '-bromo- [1,1' -biphenyl ] -3-yl) boronic acid (41.54g,150mmol), to give intermediate a: 54.23g of 2- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -1-phenyl-1H-benzimidazole, yield 85%;
(2) synthesis of intermediate b:
intermediate b was obtained by substituting a (34.92g,100mmol) in example 1(2) with a (42.53g, 100mmol) in this example and the other synthesis procedures were the same as those for intermediate b in example 1: 34.87g of 2- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -1-phenyl-1H-benzimidazole was obtained in a yield of 82%.
(3) Synthesis of intermediate c:
the synthesis of the target compound c in example 1 was carried out in the same manner as in example 1 except that b (21.99g,70mmol) in example 1(3) was replaced with b (29.77g, 70mmol) in this example, whereby the target compound c: 23.60g of the compound (121), yield 87%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 774.9463, theoretical molecular weight: 774.9460, respectively; call for C52H34N6(%) C80.60, H4.42, N10.84 Found C,80.60, H4.40, N10.85. From the mass spectrum data and the elemental analysis results, the product was correct in structure and was compound (121).
Example 7: compound (150) can be synthesized by the following method:
Figure BDA0001813665380000212
(1) intermediate a1、a2The synthesis of (2):
the iodobenzene (40.79g,200mmol) in example 1(1) was replaced by 1-iodonaphthalene (50.81g,200mmol), and the synthesis was otherwise identical to that of intermediate a in example 10The synthesis process of (1) to obtain an intermediate a10: 50.42g of 2-bromo-1- (naphthalen-1-yl) -1H-benzimidazole, yield 78%;
a in example 1(1)0(40.97g,150mmol) was replaced with a in this example10(48.48g, 150mmol), 4-bromobenzeneboronic acid (30.12g,150mmol) was replaced by (5-bromonaphthalen-1-yl) boronic acid (37.63g,150mmol), and the other synthetic procedures were the same as those of intermediate a in example 1, to give intermediate a1: 2- (5-bromonaphthalen-1-yl) -1- (naphthalen-1-yl) -1H-benzimidazole 50.55g, yield 75%;
the intermediate a can be obtained by replacing 4-bromobenzeneboronic acid (30.12g,150mmol) in example 1(1) with (5-bromonaphthalen-1-yl) boronic acid (37.63g,150mmol) and performing the same synthetic process as that of intermediate a in example 12: 46.12g of 2- (5-bromonaphthalen-1-yl) -1-phenyl-1H-benzimidazole, yield 77%.
(2) Intermediate b1、b2The synthesis of (2):
the a (34.92g,100mmol) in example 1(2) was replaced by a in this example1(44.94g, 100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b1: 32.73g of (5- (1- (naphthalen-1-yl) -1H-benzimidazol-2-yl) naphthalen-1-yl) boronic acid was obtained in 79% yield.
The a (34.92g,100mmol) in example 1(2) was replaced by a in this example2(39.93g, 100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b2: 28.77g of (5- (1-phenyl-1H-benzimidazol-2-yl) naphthalen-1-yl) phenylboronic acid (yield: 79%).
(3) Synthesis of target compound c:
b in example 2(3)1(14.15g,35mmol) was replaced with b in this example1(14.50g,35mmol) of b in example 2(3)2(13.66g,35mmol) was replaced with b in this example2(12.75g,35mmol), and the other synthesis procedures are the same as those of the target compound c in example 2, so that the target compound c: 18.94g of the compound (150) was obtained in a yield of 70%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 772.9304, theoretical molecular weight: 772.9300, respectively; call for C52H32N6(%) C80.81, H4.17, N10.87 Found C80.80, H4.19, N10.85. From the mass spectrometry data and the results of elemental analysis, the product was correct in structure and was a compound (150).
Example 8: compound (164) can be synthesized by the following method:
Figure BDA0001813665380000231
(1) intermediate a1、a2The synthesis of (2):
2-bromobenzothiazole (32.11g, 150mmol), (6-bromonaphthalen-1-yl) boronic acid (37.63g,150mmol), potassium carbonate (41.46g,300mmol), tetrahydrofuran (400mL), water (150mL) were added to a 1L three-necked flask, and tetrakis (triphenylphosphine) palladium (0.35g,0.3mmol) was further added under nitrogen protection, the temperature was raised to 85 ℃ for 10h, the reaction was monitored by HPLC for completion, and the reaction was stopped by cooling. Washing with water, filtering, concentrating the mother liquor, mixing the residue with the concentrated mother liquor, and separating with column chromatography to obtain intermediate a1: 38.28g of 2- (6-bromonaphthalen-1-yl) benzothiazole, yield 75%;
intermediate a2The synthetic process of (A) is the same as that of the intermediate a1The intermediate a was obtained by replacing (6-bromonaphthalen-1-yl) boronic acid (37.63g,150mmol) with (5-bromonaphthalen-2-yl) boronic acid (37.63g,150mmol)2: 39.30g of 2- (5-bromonaphthalen-2-yl) benzothiazole, yield 77%.
(2) Intermediate b1、b2The synthesis of (2):
the a (34.92g,100mmol) in example 1(2) was replacedIs a in the present embodiment1(34.02g, 100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b1: 24.72g of (5- (benzothiazol-2-yl) naphthalen-2-yl) boronic acid was obtained in 81% yield.
The a (34.92g,100mmol) in example 1(2) was replaced by a in this example2(34.02g, 100mmol), the other synthetic procedures were the same as those of intermediate b in example 1, to obtain intermediate b2: 24.11g of (6- (benzothiazol-2-yl) naphthalen-1-yl) boronic acid was obtained in 79% yield.
(3) Synthesis of target compound c:
b in example 2(3)1(14.15g,35mmol) was replaced with b in this example1(10.68g,35mmol) of b in example 2(3)2(13.66g,35mmol) was replaced with b in this example2(10.68g,35mmol), and the other synthesis procedures were the same as those of the objective compound c of example 2, so as to obtain the objective compound c: 15.24g of the compound (164) was obtained in a yield of 72%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 604.7634, theoretical molecular weight: 604.7640, respectively; call for C36H20N4(%) C71.50, H3.33, N9.26 Found C71.50, H3.35, N9.25. From the mass spectrum data and the elemental analysis results, the product was correct in structure and was a compound (164).
Example 9: compound (173) can be synthesized by the following method:
Figure BDA0001813665380000241
by substituting 2-bromobenzothiazole (32.11g, 150mmol) in example 8(1) with 1, 1-dioxo-2-bromobenzothiazole (36.91g, 150mmol), (6-bromonaphthalen-1-yl) boronic acid (37.63g,150mmol) with (3 '-bromo- [1,1' -phenyl ] -4-yl) boronic acid (41.54g,150mmol), the synthesis was otherwise identical to that of intermediate a of example 8, to give intermediate a: 50.78g of 1, 1-dioxo-2- (3 '-bromo- [1,1' -biphenyl ] -4-yl) benzothiazole was contained, yield 85%.
(2) Synthesis of intermediate b:
intermediate b was obtained by substituting a (34.92g,100mmol) in example 1(2) with a (39.83g, 100mmol) in this example and the other synthesis procedures were the same as those for intermediate b in example 1: 29.78g of (4'- (1, 1-dioxobenzothiazol-2-yl) - [1,1' -biphenyl ] -3-yl) boronic acid was obtained in a yield of 82%.
(3) Synthesis of target compound c:
the synthesis of the target compound c in example 1 was carried out in the same manner as in example 1 except that b (21.99g,70mmol) in example 1(3) was replaced with b (25.42g, 70mmol) in this example, whereby the target compound c: compound (173)21.95g, yield 87%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 720.8364, theoretical molecular weight: 720.8360, respectively; call for C40H24N4(%) C66.65, H3.36, N7.77 Found C66.65, H3.35, N7.78. From the mass spectrometry data and the elemental analysis results, the product was correct in structure and was compound (173).
Example 10: compound (190) can be synthesized by the following method:
Figure BDA0001813665380000242
(1) synthesis of intermediate a:
by substituting 2-bromobenzothiazole (32.11g, 150mmol) in example 8(1) with 2-bromobenzoxazole (29.70g, 150mmol), (6-bromonaphthalen-1-yl) boronic acid (37.63g,150mmol) for (7-bromonaphthalen-1-yl) boronic acid (37.63g,150mmol), the procedure of example 8 was otherwise the same as that for intermediate a, to give intermediate a: 37.44g of 2- (6-bromonaphthalen-1-yl) benzoxazole, yield 77%.
(2) Synthesis of intermediate b:
intermediate b was obtained by substituting a (34.92g,100mmol) in example 1(2) with a (32.42g, 100mmol) in this example and the other synthesis procedures were the same as those for intermediate b in example 1: 23.42g of (5- (benzoxazol-2-yl) naphthalen-2-yl) boronic acid was obtained in 81% yield.
(3) Synthesis of target compound c:
the synthesis of the target compound c in example 1 was carried out in the same manner as in example 1 except that b (21.99g,70mmol) in example 1(3) was replaced with b (20.24g, 70mmol) in this example, whereby the target compound c: compound (190)14.83g, yield 74%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 572.6417, theoretical molecular weight: 572.6420, respectively; call for C36H20N4(%) C75.51, H3.52, N9.78 Found C75.50, H3.52, N9.80. From the mass spectrometry data and the elemental analysis results, the product was correct in structure and was a compound (190).
The preparation of compounds 1-193 can be accomplished according to the procedures described in the examples for the preparation of compound samples above.
Application example 1
The device preparation which is carried out by taking the bipolar compound based on 1,3, 4-thiadiazole as the luminescent layer main body material can be prepared according to the method.
The ITO (indium tin oxide) glass substrate with the film thickness of 150nm is sequentially cleaned in a cleaning agent and deionized water for 1h by ultrasonic waves, then is continuously cleaned for 30 minutes by ultrasonic waves through acetone and isopropanol, then is dried for 2 hours in vacuum (105 ℃), then is treated by UV ozone for 15 minutes, and is conveyed to a vacuum evaporator. A layer of MoO with the following structural formula and the thickness of 60nm is evaporated on the ITO in a mode of covering an anode3(molybdenum trioxide) forms the hole injection layer. Then, NPB (N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine) having the following structural formula was deposited in a film thickness of 60nm so as to cover the hole injection layer, thereby forming a hole transport layer. Depositing a layer of doped Ir (ppy) with the thickness of 20nm on the hole transport layer3(tris (2-phenylpyridine) iridium) the bipolar compound according to the present invention forms a light-emitting layer, and Ir (ppy) in terms of mass fraction3: the bipolar compound provided by the invention is 5: 95. Next, TmPyPB (3,3'- [5' - [3- (3-pyridyl) phenyl) having the following structural formula was deposited on the light-emitting layer to cover the light-emitting layer by vapor deposition to a film thickness of 30nm][1,1':3', 1' -terphenyl]-3,3 "-diyl]Bipyridine) forms the electron transport layer. Finally, in the electricityAnd sequentially evaporating 1nm LiF (lithium fluoride) and 100nm Al (aluminum) on the sub-transport layer to form an electron injection layer and a cathode. The concrete structure is as follows: ITO/MoO3(10nm)/NPB (60 nm)/Bipolar Compound provided by the invention 5% wt Ir (ppy)3 (20nm)/TmPyPB(30nm)/LiF(1nm)/Al(100nm)。
Figure BDA0001813665380000261
Application example 2
The device preparation which is carried out by taking the bipolar compound based on 1,3, 4-thiadiazole as the luminescent layer main body material and the luminescent layer material can be prepared according to the method.
The ITO glass substrate with the film thickness of 150nm is sequentially cleaned in a cleaning agent and deionized water for 1h by ultrasonic waves, then is continuously cleaned for 30 minutes by acetone and isopropanol in sequence, then is dried for 2 hours in vacuum (105 ℃), then is treated by UV ozone for 15 minutes, and the ITO glass substrate is conveyed to a vacuum evaporator. A layer of MoO with the following structural formula and the thickness of 10nm is deposited on the ITO in a mode of covering the anode3A hole injection layer is formed. Next, a hole transport layer was formed by vapor deposition of a 60nm thick NPB layer so as to cover the hole injection layer. Depositing a layer of doped Ir (ppy) with a film thickness of 20nm on the hole transport layer3(tris (2-phenylpyridine) iridium) the bipolar compound according to the present invention forms a light-emitting layer, and Ir (ppy) in terms of mass fraction3: the bipolar compound provided by the invention is 5: 95. Next, an electron transport layer was formed by vapor-plating TmPyPB having a film thickness of 30nm on the light-emitting layer so as to cover the light-emitting layer. Then, 1nm LiF and 100nm Al were sequentially evaporated on the electron transport layer to form an electron injection layer and a cathode. And finally, evaporating the bipolar compound with the film thickness of 10nm on the cathode in a mode of covering the cathode to form a light emitting layer. The concrete structure is as follows: ITO/MoO3(10nm)/NPB (60 nm)/Bipolar Compound provided by the invention 5% wt Ir (ppy)3(20nm)/TmPyPB (30nm)/LiF (1nm)/Al (100 nm)/the bipolar compound (10nm) provided by the invention.
Application example 3
The device preparation which is carried out by taking the bipolar compound based on 1,3, 4-thiadiazole as the material of the light-emitting layer can be prepared according to the method.
The ITO glass substrate with the film thickness of 150nm is sequentially cleaned in a cleaning agent and deionized water for 1h by ultrasonic waves, then is continuously cleaned for 30 minutes by acetone and isopropanol in sequence, then is dried for 2 hours in vacuum (105 ℃), then is treated by UV ozone for 15 minutes, and the ITO glass substrate is conveyed to a vacuum evaporator. A layer of MoO with the following structural formula and the thickness of 10nm is deposited on the ITO in a mode of covering the anode3A hole injection layer is formed. Next, a hole transport layer was formed by vapor deposition of a 60nm thick NPB layer so as to cover the hole injection layer. Depositing a layer of doped Ir (ppy) with a film thickness of 20nm on the hole transport layer3CBP (4,4' -bis (9-carbazole) biphenyl) having the following structural formula (I) forms a light-emitting layer, in terms of mass fraction, Ir (ppy)3: the CBP was 5: 95. Next, an electron transport layer was formed by vapor-plating TmPyPB having a film thickness of 30nm on the light-emitting layer so as to cover the light-emitting layer. Then, 1nm LiF and 100nm Al were sequentially evaporated on the electron transport layer to form an electron injection layer and a cathode. Finally, a layer of the bipolar compound provided by the invention with the thickness of 10nm is deposited on the cathode in a mode of covering the cathode to form a light emitting layer. The concrete structure is as follows: ITO/MoO3(10nm)/NPB (60nm)/CBP:5％wt Ir(ppy)3(20nm)/TmPyPB (30nm)/LiF (1nm)/Al (100 nm)/the bipolar compound (10nm) provided by the invention.
Figure BDA0001813665380000271
Comparative examples
The ITO glass substrate with the film thickness of 150nm is sequentially cleaned in a cleaning agent and deionized water for 1h by ultrasonic waves, then is continuously cleaned for 30 minutes by acetone and isopropanol in sequence, then is dried for 2 hours in vacuum (105 ℃), then is treated by UV ozone for 15 minutes, and the ITO glass substrate is conveyed to a vacuum evaporator. To cover the anodeA layer of MoO with the following structural formula and the thickness of 10nm is evaporated on the ITO3A hole injection layer is formed. Next, a hole transport layer was formed by vapor deposition of a 60nm thick NPB layer so as to cover the hole injection layer. Depositing a layer of doped Ir (ppy) with a film thickness of 20nm on the hole transport layer3CBP (4,4' -bis (9-carbazole) biphenyl) of tris (2-phenylpyridine) iridium forms a light-emitting layer, and Ir (ppy) in mass fraction3: the CBP was 5: 95. Next, an electron transport layer was formed by vapor-plating TmPyPB having a film thickness of 30nm on the light-emitting layer so as to cover the light-emitting layer. Then, 1nm LiF and 100nm Al were sequentially evaporated on the electron transport layer to form an electron injection layer and a cathode. Finally, a layer of the bipolar compound provided by the invention with the thickness of 10nm is deposited on the cathode in a mode of covering the cathode to form a light emitting layer. The concrete structure is as follows: ITO/MoO3(10nm)/NPB (60nm)/CBP:5％wt Ir(ppy)3(20nm)/TmPyPB(30nm)/LiF(1nm)/Al(100nm)。
The measurement results of the light emission characteristics when the organic electroluminescent device fabricated according to the above embodiment is applied with a dc voltage are summarized in table 1:
TABLE 1 characterization of organic electroluminescent device Properties
Figure BDA0001813665380000281
Figure BDA0001813665380000291
As can be seen from the table, the 1,3, 4-thiadiazole-based bipolar compound provided by the invention can be used as a light-emitting layer material to remarkably improve the light extraction efficiency of a device, and the performances of the device in the aspects of luminous intensity, current efficiency, power efficiency and external quantum efficiency are remarkably improved, so that the material is an ideal light-emitting layer material. In addition, the bipolar compound based on 1,3, 4-thiadiazole provided by the invention has excellent performance in the application of a luminescent layer main body material, can effectively realize bright and uniform green light, and improves the comprehensive performance of the device in the aspects of starting voltage, luminous brightness, current efficiency, power efficiency, external quantum efficiency and the like.
It should be noted that, as shown in the wavelength-light intensity characteristic graph shown in fig. 2, the device 4 prepared by using the bipolar compound based on 1,3, 4-thiadiazole as the light emitting layer host material and the device 14 prepared by using the bipolar compound as the light emitting layer host material and the light emitting layer material independently emit pure saturated green light. As shown in FIGS. 3 and 4, compared with the existing device 20 prepared by taking CBP as the main material of the light-emitting layer, the device 4 prepared by independently taking the bipolar compound based on 1,3, 4-thiadiazole as the main material of the light-emitting layer provided by the invention has balanced charge transport capability and high-efficiency carrier recombination transition, so that the brightness of the device reaches 59040cd/m2The current efficiency and the power efficiency respectively reach 128.62cd/A and 111.94lm/W, the comprehensive performance of the device is improved, compared with the device 4 without the light-emitting layer, the device 14 prepared by using the light-emitting layer material has obviously improved light extraction efficiency, and the brightness of the device reaches 67750cd/m2The current efficiency reaches 153.45cd/A, the power efficiency reaches 145.32lm/W, and the problem of light dissipation in the device is effectively solved. As shown in the graph of luminance-external quantum efficiency characteristic shown in fig. 5, in comparison with the existing device 20 prepared by using CBP as the light-emitting layer host material, the device 4 prepared by using the 1,3, 4-thiadiazole-based bipolar compound as the light-emitting layer host material independently improves the external quantum efficiency to a certain extent, and when the 1,3, 4-thiadiazole-based bipolar compound provided by the present invention is added as the light-emitting layer structure to prepare the device 14, the light extraction efficiency is improved to a great extent, the external quantum efficiency can be improved by more than 30%, and the roll reduction problem of the device is greatly improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. The bipolar compound based on 1,3, 4-thiadiazole is characterized by having a structural general formula as shown in the following (I):
Figure FDA0003459715870000011
wherein Ar is1、Ar2Independently are: any one of substituted or unsubstituted arylene groups having 6 to 24 carbon atoms, Ar1、Ar2The same or different;
R1、R2、R3、R4、R5、R6、R7、R8independently are: any one of hydrogen, an alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted or unsubstituted heterocyclic group having 5 to 12 carbon atoms, R1、R2、R3、R4、R5、R6、R7、R8The same or different;
X1、X2independently are: s, O-S-O, O or N-L;
wherein L is selected from: any one of a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 6 to 24 carbon atoms, a substituted or unsubstituted fluorenyl group having 12 to 24 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 24 carbon atoms, X1、X2The same or different;
when said Ar is1、Ar2Independently are: when any one of the substituted arylene groups having a carbon number of 6 to 24 is used, the substituent of the arylene group is selected from: any one of an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 10 carbon atoms;
when said R is1、R2、R3、R4、R5、R6、R7、R8Independently are: when any one of a substituted aryloxy group having 6 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms, and a substituted heterocyclic group having 5 to 12 carbon atoms is used, the substituents for the aryloxy group, the aryl group, and the heterocyclic group are independently selectedFrom: any one of an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 10 carbon atoms;
when said L is selected from: when any one of a substituted aryl group having 6 to 24 carbon atoms, a substituted aromatic heterocyclic group having 6 to 24 carbon atoms, a substituted fluorenyl group having 12 to 24 carbon atoms, and a substituted arylamine group having 6 to 24 carbon atoms is used, the substituents for the aryl group, the aromatic heterocyclic group, the fluorenyl group, and the arylamine group are each independently selected from the group consisting of: an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
2. The 1,3, 4-thiadiazole-based bipolar compound of claim 1, wherein said R is1、R2、R3、R4、R5、R6、R7、R8All hydrogen, the structural general formula of the bipolar compound is shown as the following (II):
Figure FDA0003459715870000021
3. the 1,3, 4-thiadiazole-based bipolar compound of claim 1, wherein said Ar is1、Ar2Each independently selected from: any one of phenylene group unsubstituted, substituted with an alkyl group having a carbon number of 1 to 4 or substituted with an aryl group having a carbon number of 6 to 10, any one of biphenylene group unsubstituted, substituted with an alkyl group having a carbon number of 1 to 4 or substituted with an aryl group having a carbon number of 6 to 10, or any one of naphthylene group unsubstituted, substituted with an alkyl group having a carbon number of 1 to 4 or substituted with an aryl group having a carbon number of 6 to 10.
4. The 1,3, 4-thiadiazole-based bipolar compound of claim 1, wherein said X is1、X2Are respectively N-L, wherein, the X is1、X2The corresponding L is independently selected from: unsubstituted, substituted by alkyl groups having a carbon number of 1 to 4 or by aryl groups having a carbon number of 6 to 10Any one of substituted aryl groups having 6 to 24 carbon atoms, any one of aromatic heterocyclic groups having 6 to 24 carbon atoms which are unsubstituted, substituted with alkyl groups having 1 to 4 carbon atoms or substituted with aryl groups having 6 to 10 carbon atoms, or any one of fluorenyl groups having 12 to 24 carbon atoms which are unsubstituted or substituted with aryl groups having 6 to 10 carbon atoms.
5. The 1,3, 4-thiadiazole-based bipolar compound of claim 4, wherein said X is1、X2Each independently selected from any one of the following structures:
Figure FDA0003459715870000031
6. a process for the preparation of 1,3, 4-thiadiazole-based bipolar compounds according to any one of claims 1 to 5, comprising the following scheme:
Figure FDA0003459715870000041
the synthesis steps are as follows:
s1, intermediate A10、Ar1Feeding the corresponding substituted halogenated boric acid derivative and potassium carbonate according to the molar ratio of 1 (1-3) to 2-4, and adding the intermediate A10: toluene: ethanol: water 1 mmol: 1-4 mL: 1-4 mL: adding 1-4mL of toluene, ethanol and water, and adding the intermediate A under the protection of nitrogen10Adding 1 per mill-5% of tetrakis (triphenylphosphine) palladium, heating to 60-100 deg.C, reacting for 6-30h to obtain intermediate A1；
Intermediate A20、Ar2Feeding the corresponding substituted halogenated boric acid derivative and potassium carbonate according to the molar ratio of 1 (1-3) to 2-4, and adding the intermediate A20: toluene: ethanol: water 1 mmol: 1-4 mL: 1-4 mL: adding toluene, ethanol and water into 1-4mL of the mixture under the protection of nitrogen according to the methodThe intermediate A20Adding 1 per mill-5% of tetrakis (triphenylphosphine) palladium, heating to 60-100 deg.C, reacting for 6-30h to obtain intermediate A2；
S2, intermediate A according to1: tetrahydrofuran was 1 mmol: 2-5mL of the intermediate A1Dissolving in tetrahydrofuran, cooling to-78 deg.C under nitrogen protection, stirring for 0.3-2h, mixing with n-butyllithium cyclohexane solution and the intermediate A1The ratio is 0.2-4mL: after 1mmol addition and reaction for 0.5-3h, as described for intermediate A1Adding 1-3 times of triethyl borate, continuing to react for 1-4h, heating to room temperature, reacting for 6-20h, cooling to 0 ℃, and adding the intermediate A1: hydrochloric acid 1 mmol: 0.2-4mL of hydrochloric acid solution is added for hydrolysis reaction, and an intermediate B is obtained after treatment1；
According to said intermediate A2: tetrahydrofuran was 1 mmol: 2-5mL of the intermediate A2Dissolving in tetrahydrofuran, cooling to-78 deg.C under nitrogen protection, stirring for 0.3-2h, mixing with n-butyllithium cyclohexane solution and the intermediate A2Adding 1mmol of the intermediate A according to the proportion of 0.2-4mL and reacting for 0.5-3h2Adding 1-3 times of triethyl borate, continuing to react for 1-4h, heating to room temperature, reacting for 6-20h, cooling to 0 ℃, and adding the intermediate A2: hydrochloric acid 1 mmol: 0.2-4mL of hydrochloric acid solution is added for hydrolysis reaction, and an intermediate B is obtained after treatment2；
S3 and the intermediate B1Feeding 2-bromo-5-chloro-1, 3, 4-thiadiazole and potassium carbonate according to the molar ratio of 1 (1-3) to 2-4, and adding the intermediate B1: toluene: ethanol: water 1 mmol: 1-10 mL: 1-10 mL: adding 1-10mL of toluene, ethanol and water, and adding the intermediate B under the protection of nitrogen1Adding 1 per mill-5% of tetrakis (triphenylphosphine) palladium, heating to 60-100 deg.C, reacting for 4-30h, returning to room temperature, and adding into intermediate B1In an amount of 1 to 3 times the amount of the intermediate B2Heating to 60-100 ℃ for reaction for 6-30h, and processing to obtain the target compound C after the reaction is finished.
7. An organic light-emitting element comprising: an anode, a cathode and a light extraction layer, wherein the material of the light extraction layer comprises the 1,3, 4-thiadiazole-based bipolar compound as claimed in any one of claims 1 to 5, and the light extraction layer is stacked on the cathode, and the cathode is stacked on the anode.
8. The organic light-emitting element according to claim 7, further comprising a light-emitting layer sandwiched between the anode and the cathode, wherein a material of the light-emitting layer comprises the 1,3, 4-thiadiazole-based bipolar compound according to any one of claims 1 to 5.
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