CN109053680B - Organic small-molecule photoelectric functional material based on 3-benzoylpyridine as receptor unit, and preparation method and application thereof - Google Patents
Organic small-molecule photoelectric functional material based on 3-benzoylpyridine as receptor unit, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic micromolecular photoelectric functional material based on 3-benzoylpyridine as an acceptor unit, which is mainly attached to the hydrogen bond effect of nitrogen in the benzoylpyridine and can effectively avoid the defect of radiation rate reduction caused by a large torsion angle, thereby improving the horizontal molecular orientation, and realizing the simplification of a device structure and the improvement of the device performance and service life. Meanwhile, the inherent characteristics of the material, such as molecular weight, conjugation length, charge transfer and the like, can be effectively adjusted by regulating the type and size of the donor connecting unit. The invention also discloses a preparation method and application of the material. The organic micromolecule photoelectric material taking 3-benzoylpyridine as the acceptor unit has the advantages of high radiation rate constant, high quantum efficiency and high carrier transmission performance, and has the advantages of adjustable chromaticity, high efficiency, stability, long service life and the like when being used as a light emitting layer of an organic electroluminescent device.
Description
Technical Field
The invention relates to the technical field of materials of organic photoelectric devices, in particular to an organic micromolecule photoelectric functional material based on 3-benzoylpyridine as a receptor unit, and a preparation method and application thereof.
Background
In order to improve the efficiency and the service life of an organic photoelectric device, compared with a polymer luminescent material, small organic molecules have the advantages of simple preparation, stable structure and convenient purification, so that higher device efficiency can be obtained, and the organic photoelectric device is close to commercial application.
In recent years, a thermal activation delay mechanism fluorescent material is widely applied to an O L ED device, the material can effectively get rid of the intramolecular spin coupling effect of the traditional fluorescent material, and meanwhile, singlet excitons with the generation probability of 25% and triplet excitons with the generation probability of 75% are utilized, so that the luminous efficiency is greatly improved.
It has been disclosed that benzophenone-Based Derivatives [ H.ZHAO, Z.Wang, X.Cai, S.J.Su, high Efficiency chemical engineering Materials with reduced Efficiency and L ow On-Set volts 2017,1, 2039. minus 2046; S.Oh, K.H. L ee, J.H.Seo, S.S.Yoon, high Efficiency Blue L, Emitting Materials with aryl amine treated under treated surface, stabilized by pyridine, Na.S.J.S.J.S.J.S.J.S.J.S.J.A. Pat. No. 5. J.S.J.S.J.S.J.S.J.S.J.S.J.S.S.J.S.P.A.A.A.A. Pat. No. 5. and No. 10. A.S.S.J.S.J.S.J.S.J.S.S.J.S.S.J.S.S.S.J.P.S.S.S.S.J.S.S.S.J.P.S.C.S.S.S.S.S.S.S.S.S.S.S.S.S.J.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.materials.S.S.S.S.S.S.S.S.S.S.S.S.materials, and No. Materials, and No. Pat. No. Materials, and No. Pat. Materials, S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide an organic micromolecular photoelectric functional material based on 3-benzoylpyridine as an acceptor unit, which has the characteristics of high quantum efficiency and high carrier transport performance.
The invention also aims to provide a preparation method of the organic micromolecule photoelectric functional material taking 3-benzoylpyridine as an acceptor unit.
The invention further aims to provide application of the organic micromolecule photoelectric functional material taking 3-benzoylpyridine as an acceptor unit.
The purpose of the invention is realized by the following technical scheme:
the organic micromolecular photoelectric functional material based on 3-benzoyl pyridine as an acceptor unit has the following structural general formula:
wherein:
r is selected from aromatic amine units shown in (1) to (35):
the organic micromolecular photoelectric functional material based on 3-benzoylpyridine as the receptor unit mainly depends on the hydrogen bond action of nitrogen in the benzoylpyridine, and can effectively avoid the reduction of radiation rate caused by a large torsion angle, thereby improving the horizontal molecular orientation, and realizing the simplification of the device structure and the improvement of the device performance and service life. Meanwhile, the material characteristics such as molecular weight, conjugation length, charge transfer and the like of the material can be effectively adjusted by regulating the type and size of the donor connecting unit. The preparation method of the invention uses the conventional bromobenzene and p-bromoaldehyde pyridine as initial reaction raw materials, and then obtains the target compound through a series of simple reactions; has high thermal degradation temperature and proper sublimation temperature, and is easy to sublimate and purify. The material of the invention has the advantages of adjustable chromaticity, high efficiency, stability, long service life and the like when being used as a luminescent layer of an organic electroluminescent device.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the organic micromolecule material taking 3-benzoylpyridine as the receptor nucleus unit has the advantages of simple structure, definite molecular weight, easy purification, good electrochemical stability and easy research of structure-activity relationship.
(2) The organic small molecular material taking 3-benzoylpyridine as an acceptor core unit has larger molecular horizontal orientation, high fluorescence quantum yield, and can realize lower efficiency roll-off while presenting the property of thermally activated delayed fluorescence.
(3) The invention takes 3-benzoyl pyridine as the acceptor nuclear unit coupling donor aromatic amine, and can further develop the stable luminescence mechanism of the material, optimize the material performance and improve the service life of the device through the hydrogen bond action of the nitrogen action site.
(4) The invention also has the more important advantages that compared with the benzophenone without nitrogen action site as the acceptor nuclear small molecular material, the organic small molecular material which takes the 3-benzoylpyridine as the acceptor nuclear unit and is proved by taking the same compound as the donor has lower lighting voltage, higher current density, more excellent external quantum efficiency and more stable device life.
(5) The invention uses 3-benzoyl pyridine as receptor nucleus unit, which can change the kind and size of the coupled donor unit, the number of sites and the number of generations (such as carbazole), to effectively regulate and control the light color and efficiency of the material, and meet the demand of organic photoelectric device.
Drawings
FIG. 1 is the absorption and emission spectra of compound P16 in toluene solution;
FIG. 2 is the electrochemical stability of Compound P16, repeated redox scans 100 times;
FIG. 3 is a graph showing the relationship between current density, voltage and luminance of the organic light emitting diode device to which the compound P16 of example 16 was applied;
FIG. 4 is a graph showing the relationship between current efficiency, luminance and external quantum efficiency of the compound P16 of example 16 applied to an organic light emitting diode device;
FIG. 5 is the electroluminescence spectrum of compound P16 in example 16.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The reaction formula of compound P1 is shown below:
the specific reaction steps are as follows:
reacting (6-bromopyridin-3-yl) (phenyl) methanone (1.5mmol,390mg), carbazole (1.6mmol,270mg), cuprous iodide(0.075mmol,18mg), 1, 10-phenanthroline (0.075mmol,11mg) and anhydrous sodium carbonate (3mmol,415mg) are sequentially added into a reaction bottle, nitrogen is pumped for 3 times, then P-xylene (10 m L) is added through a syringe, reflux reaction is carried out at 150 ℃ for 24 hours under the condition of nitrogen, after the reaction is finished, the system is recovered to room temperature, dichloromethane and saturated saline solution are used for extraction and washing, the organic phase is recovered and dried by anhydrous magnesium sulfate, the solvent is removed by reduced pressure distillation, then the crude product is separated and purified by column chromatography, the eluent is petroleum ether/dichloromethane 3:1, and finally the compound P1 product is obtained, the yield is 78%, and the molecular formula of the product is C24H16N2O; 348.13 molecular weight m/z; the elemental analysis results were: c, 72.74; h, 4.63; n, 8.04; and O, 4.59.
Example 2
The reaction formula of compound P2 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to diphenylamine with equivalent amount, other raw materials and procedures were the same as in example 1, and compound P2 was finally obtained with a yield of 75%. The molecular formula of the product is as follows: c24H18N2O; 350.16 molecular weight m/z; the elemental analysis results were: c, 82.26; h, 5.18; n, 7.99; and O, 4.57.
Example 3
The reaction formula of compound P3 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that the carbazole was changed to phenoxazine with equivalent amount, other raw materials and procedures were the same as in example 1, and finally compound P3 was obtained in 73% yield. The molecular formula of the product is as follows: c24H16N2O2(ii) a 365.16 molecular weight m/z; the elemental analysis results were: c, 79.11;H,4.43；N,7.69；O,8.78。
example 4
The reaction formula for chemical P4 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to phenothiazine with equivalent amount, other raw materials and procedures were the same as example 1, compound P3 was finally obtained with a yield of 67%. The molecular formula of the product is as follows: c24H16N2An OS; 381.10 molecular weight m/z; the elemental analysis results were: c, 75.77; h, 4.24; n, 7.36; o, 4.21; s, 8.43.
Example 5
The reaction formula of compound P5 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was replaced by equivalent 10H-phenothiazine 5, 5-dioxide, other raw materials and procedures were the same as example 1, compound P5 was finally obtained in 76% yield. The molecular formula of the product is as follows: c24H16N2O3S; 412.09 molecular weight m/z; the elemental analysis results were: c, 69.89; h, 3.91; n, 6.79; o, 11.64; s, 7.77.
Example 6
The reaction formula of compound P6 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was replaced by equivalent 9,9-dimethyl-9, 10-dihydroacridine, and other raw materials and procedures were the same as those of example 1, compound P6 was finally obtained in 86% yield. The molecular formula of the product is as follows: C27H22N 2O; 390.17 molecular weight m/z; the elemental analysis results were: c, 83.05; h, 5.68; n, 7.17; and O, 4.10.
Example 7
The reaction formula of compound P7 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was replaced by equivalent 10,10-dimethyl-5,10-dihydrodibenzo [ b, e ] [1,4] azasine, and other raw materials and procedures were the same as in example 1, compound P7 was finally obtained with a yield of 83%. The molecular formula of the product is as follows: C26H22N2 OSi; 406.15 molecular weight m/z; the elemental analysis results were: c, 76.81; h, 5.45; n, 6.89; o, 3.94; si, 6.91.
Example 8
The reaction formula of compound P8 is shown below:
the specific reaction steps are as follows:
the difference from example 1 was that carbazole was replaced with an equivalent amount of acridin-9-10H-ketone and the other starting materials and procedures were the same as in example 1, to give the compound P8 in 76% yield. The molecular formula of the product is as follows: C25H16N2O 2; the molecular weight m/z is 376.12; the elemental analysis results were: c, 79.77; h, 4.28; n, 7.44; and O, 8.50.
Example 9
The reaction formula of compound P9 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that the carbazole was changed to equivalent 3, 6-di-tert-butylcarbazole, the other raw materials and procedures were the same as in example 1, and finally compound P9 was obtained in 73% yield. The molecular formula of the product is as follows: C32H32N 2O; 461.25 molecular weight m/z; the elemental analysis results were: c, 83.44; h, 7.00; n, 6.08; and O, 3.47.
Example 10
The reaction formula of compound P10 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent amount of bis (4-tert-butylphenyl) amine, other raw materials and procedures were the same as in example 1, and compound P10 was finally obtained in 63% yield. The molecular formula of the product is as follows: C34H34N 2O; 463.27 molecular weight m/z; the elemental analysis results were: c, 83.08; h, 7.41; n, 6.06; and O, 3.46.
Example 11
The reaction formula of compound P11 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that the carbazole was changed to equivalent 3, 6-dimethoxy-9H-carbazole, the other raw materials and procedures were the same as in example 1, and finally compound P11 was obtained in 73% yield. The molecular formula of the product is as follows: C26H20N2O 3; 409.15 molecular weight m/z; the elemental analysis results were: c, 76.46; h, 4.94; n, 6.86; and O, 11.75.
Example 12
The reaction formula of compound P12 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to 5-phenyl-5, 10-dihydro with equivalent amount, other raw materials and procedures were the same as example 1, compound P12 was finally obtained with a yield of 71%. The molecular formula of the product is as follows: C30H21N 3O; 439.17 molecular weight m/z; the elemental analysis results were: c, 81.98; h, 4.82; n, 9.56; and O, 3.64.
Example 13
The reaction formula of compound P13 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was replaced by equivalent 10H-spiro [ acridine-9, 9' -fluorene ], other raw materials and procedures were the same as in example 1, to finally obtain compound P13 with a yield of 77%. The molecular formula of the product is as follows: C37H24N 2O; 513.19 molecular weight m/z; the elemental analysis results were: c, 86.69; h, 4.72; n, 5.46; and O, 3.12.
Example 14
The reaction formula of compound P14 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was replaced by equivalent 9, 9-diphenyl-9, 10-dihydroacridine, and other raw materials and procedures were the same as those of example 1, compound P14 was finally obtained in 68% yield. The molecular formula of the product is as follows: C37H26N 2O; 514.21 molecular weight m/z; the elemental analysis results were: c, 86.35; h, 5.09; n, 5.44; and O, 3.11.
Example 15
The reaction formula of compound P15 is shown below:
the specific reaction steps are as follows:
the difference from example 1 was that carbazole was replaced with equivalent amount of 10H-spiro [ acridine-9, 9' -xanthene ], and other raw materials and procedures were the same as in example 1, to finally obtain compound P15 in 73% yield. The molecular formula of the product is as follows: C37H24N2O 2; 528.17 molecular weight m/z; the elemental analysis results were: c, 84.07; h, 4.58; n, 5.30; and O, 6.05.
Example 16
The reaction formula of compound P16 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was replaced by equivalent 10H-spiro [ acridine-9, 9' -thioxanthene ], other raw materials and procedures were the same as in example 1, to finally obtain compound P16 with a yield of 76%. The molecular formula of the product is as follows: C37H24N2 OS; 544.16 molecular weight m/z; the elemental analysis results were: c, 81.59; h, 4.44; n, 5.14; o, 2.94; and S, 5.89.
The absorption and emission spectrum of compound P16 in toluene solution is shown in FIG. 1, and it can be seen that the stronger vertical transition absorption peak of compound P16 at 375nm is due to strong charge transfer in the donor-acceptor molecule, and a single emission peak is shown at 515 nm.
The electrochemical stability test result of the compound P16 is shown in fig. 2, the obtained compound P16 has a moderate HOMO energy level, and after cyclic scanning for 120 times, the current-voltage curve has no obvious change, which reveals that the compound P16 has very strong electrochemical stability.
The current density-voltage-luminance relationship curve of the compound P16 applied to the organic light emitting diode device is shown in fig. 3, and the electroluminescent device (example 33) has very good hole injection and transport capabilities, and the maximum luminance can achieve 12139 candelas per square meter.
The graph of the current efficiency-luminance-external quantum efficiency relationship of compound P16 applied to an organic light emitting diode device is shown in fig. 4, and the maximum current efficiency of the electroluminescent device (example 33) is 67.5 candela/ampere and the maximum external quantum efficiency is 24.3%.
The electroluminescence spectrum of compound P16, as shown in fig. 5, showed that no secondary emission peak was observed in the electroluminescence spectrum, indicating that the light-emitting device (example 33) achieved sufficient transfer of host and guest energies.
Example 17
The reaction formula of compound P17 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was replaced by equivalent 10H-spiro [ acridine-9, 9' -thioxanthene ]10',10' -dioxide, and other raw materials and procedures were the same as in example 1, compound P17 was finally obtained in 77% yield. The molecular formula of the product is as follows: C37H24N2O 3S; 576.16 molecular weight m/z; the elemental analysis results were: c, 77.06; h, 4.20; n, 4.86; o, 8.32; and S, 5.56.
Example 18
The reaction formula of compound P18 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent of 10',10' -dimethyl 10H,10 'H-spiro [ acridine-9, 9' -anthracene ], other raw materials and procedures were the same as example 1, and compound P18 was finally obtained in 64% yield. The molecular formula of the product is as follows: C40H30N 2O; 554.25 molecular weight m/z; the elemental analysis results were: c, 86.61; h, 5.45; n, 5.05; o, 2.88.
Example 19
The reaction formula of compound P19 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole is replaced by equivalent 5',5' -dimethyl-5'H,10H-spiro [ acridine-9,10' -dibezo [ b, e ] sine ], other raw materials and procedures are the same as example 1, and the compound P19 is finally obtained with 79% yield. The molecular formula of the product is as follows: C39H30N2 OSi; 570.22 molecular weight m/z; the elemental analysis results were: c, 82.07; h, 5.30; n, 4.91; o, 2.80; si, 4.92.
Example 20
The reaction formula of compound P20 is shown below:
the specific reaction steps are as follows:
the difference from example 1 was that carbazole was replaced with an equivalent amount of 10H,10' H-spiro [ acridine-9, 9' -anthracene ] -10' one and the other starting materials and procedures were the same as in example 1 to give the compound P20 in 85% yield. The molecular formula of the product is as follows: C38H24N2O 2; 540.18 molecular weight m/z; the elemental analysis results were: c, 84.42; h, 4.47; n, 5.18; and O, 5.92.
Example 21
The reaction formula of compound P21 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent 9H-3,9' -bicarbazole, other raw materials and procedures were the same as in example 1, compound P21 was finally obtained in 73% yield. The molecular formula of the product is as follows: C36H23N 3O; 513.18 molecular weight m/z; the elemental analysis results were: c, 84.19; h, 4.51; n, 8.18; and O, 3.12.
Example 22
The reaction formula of compound P22 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent amount of N, N-diphenyl-9H-carbazol-3-amine, and other raw materials and procedures were the same as example 1, compound P22 was finally obtained in 75% yield. The molecular formula of the product is as follows: C36H25N 3O; 515.27 molecular weight m/z; the elemental analysis results were: c, 83.86; h, 4.89; n, 8.15; and O, 3.10.
Example 23
The reaction formula of compound P23 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent 3',6' -di-tert-butyl-9H-3,9' -bicarbazole, and other raw materials and procedures were the same as example 1, compound P23 was finally obtained in 63% yield. The molecular formula of the product is as follows: C44H39N 3O; 625.31 molecular weight m/z; the elemental analysis results were: c, 84.45; h, 6.28; n, 6.71; o, 2.56.
Example 24
The reaction formula of compound P24 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent amount of N, N-bis (4-tert-butyl) phenyl-9H-carbazole-3-amine, and other raw materials and procedures were the same as example 1, compound P24 was finally obtained in 63% yield. The molecular formula of the product is as follows: C44H41N 3O; 627.83 molecular weight m/z; the elemental analysis results were: c, 84.18; h, 6.58; n, 6.69; o, 2.55.
Example 25
The reaction formula of compound P25 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent 3',6' -dimethoxy-9H-3,9' -dicarbazole, and other raw materials and procedures were the same as example 1, compound P25 was finally obtained in 67% yield. The molecular formula of the product is as follows: C38H27N3O 3; 573.23 molecular weight m/z; the elemental analysis results were: c, 79.56; h, 4.74; n, 7.33; o, 8.37.
Example 26
The reaction formula of compound P26 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent 9H-3,9':3', 9' -tercarbazole, and other raw materials and procedures were the same as example 1, compound P26 was finally obtained in 62% yield. The molecular formula of the product is as follows: C48H30N 4O; 678.25 molecular weight m/z; the elemental analysis results were: c, 84.93; h, 4.45; n, 8.25; o, 2.36.
Example 27
The reaction formula of compound P27 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent of N, N-diphenyl-9H- [3,9'-bicarbazol ] -3' -amine, other raw materials and procedures were the same as example 1, compound P27 was finally obtained in 67% yield. The molecular formula of the product is as follows: C48H32N 4O; 680.26 molecular weight m/z; the elemental analysis results were: c, 84.68; h, 4.74; n, 8.23; o, 2.35.
Example 28
The reaction formula of compound P28 is shown below:
the specific reaction steps are as follows:
compared with the example 1, the difference is that the carbazole is replaced by equivalent 3',6' -dimethoxy-9-methyl-4 ' a, 9' a-dihydro-9H-3,9':3', 9' -tercarbazole, and other raw materials and steps are the same as the example 1, and the compound P28 is finally obtained with the yield of 63%. The molecular formula of the product is as follows: C56H46N 4O; 790.37 molecular weight m/z; the elemental analysis results were: c, 85.03; h, 5.86; n, 7.08; and O, 2.02.
Example 29
The reaction formula of compound P29 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent N, N-bis (4- (tert-butyl) phenyl) -9H- [3,9'-bicarbazol ] -3' -amine, and other raw materials and procedures were the same as example 1, compound P29 was finally obtained in 63% yield. The molecular formula of the product is as follows: C56H48N 4O; 792.38 molecular weight m/z; the elemental analysis results were: c, 84.82; h, 6.10; n, 7.07; and O, 2.02.
Example 30
The reaction formula of compound P30 is shown below:
the specific reaction steps are as follows:
compared with the example 1, the difference is that the carbazole is replaced by equivalent 3',6' -dimethoxy-9-methyl-4 ' a, 9' a-dihydro-9H-3,9':3', 9' -tercarbazole, and other raw materials and steps are the same as the example 1, and the compound P30 is finally obtained with the yield of 63%. The molecular formula of the product is as follows: C50H36N4O 3; 740.28 molecular weight m/z; the elemental analysis results were: c, 81.06; h, 4.90; n, 7.56; and O, 6.48.
Example 31
The reaction formula of compound P31 is shown below:
the specific reaction steps are as follows:
compared with the example 1, except that the carbazole is changed into equivalent 9'H-9,3' 6', 9' -tricarbazole, other raw materials and steps are the same as the example 1, and the compound P31 is finally obtained with the yield of 71 percent. The molecular formula of the product is as follows: C48H30N 4O; 679.25 molecular weight m/z; the elemental analysis results were: c, 84.93; h, 4.45; n, 8.25; o, 2.36.
Example 32
The reaction formula of compound P32 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent of N3, N3, N6, N6-tetraphenyl-9H-carbazole-3, 6-diamine, and other raw materials and procedures were the same as example 1, compound P32 was finally obtained in 62% yield. The molecular formula of the product is as follows: C48H34N 4O; 682.83 molecular weight m/z; the elemental analysis results were: c, 84.43; h, 5.02; n, 8.21; o, 2.34.
Example 33
The reaction formula of compound P33 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent 9'H-9,3' 6', 9' -tri-tert-butylcarbazole, other raw materials and procedures were the same as example 1, compound P33 was finally obtained with a yield of 77%. The molecular formula of the product is as follows: C64H62N 4O; 902.51 molecular weight m/z; the elemental analysis results were: c, 85.11; h, 6.92; n, 6.20; o, 1.77.
Example 34
The reaction formula of compound P34 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent of N3, N3, N6, N6-tetrakis (4- (tert-butyl) phenyl) -9H-carbazole-3, 6-diamine, and other raw materials and procedures were the same as example 1, compound P34 was finally obtained in 68% yield. The molecular formula of the product is as follows: C64H66N 4O; 906.53 molecular weight m/z; the elemental analysis results were: c, 84.73; h, 7.33; n, 6.18; o, 1.76.
Example 35
The reaction formula of compound P35 is shown below:
the specific reaction steps are as follows:
compared with example 1, except that carbazole was changed to equivalent of 3,3 ", 6, 6" -tetramethoxy-9' H-9,3':6',9 "-tercarbazole, and other raw materials and procedures were the same as example 1, compound P35 was finally obtained in 56% yield. The molecular formula of the product is as follows: C52H38N4O 5; 798.28 molecular weight m/z; the elemental analysis results were: c, 78.18; h, 4.79; n, 7.01; and O, 10.01.
The compounds used in the examples of the present invention described above are not all commercially available. Wherein the aromatic amine compounds (1) - (12) are purchased from Beijing J & K, Beijing Innochem, Shanghai TCI, Shanghai Chemhere, and Hangzhou MolCore. Methods for preparing intermediates involved in the aromatic amine compounds 13 to 35 will be further described in the following examples, but embodiments of the intermediates of the present invention are not limited thereto.
Preparation of intermediate compound 13:
this example prepares an intermediate aromatic amine compound 13, having the formula for compound P and the synthetic route as follows:
the specific reaction steps are as follows:
dissolving 10mmol of 2-bromodiphenylamine in 30M L tetrahydrofuran at the low temperature of-78 ℃, slowly adding 4M L n-butyllithium (2.5M), stirring for 1 hour, then adding 10mmol of 9-fluorenone, continuously stirring for 30 minutes, recovering the temperature of room temperature, removing the solvent, dispersing in acetic acid, continuously stirring for 5 hours at 70 ℃, after the reaction is finished, recovering the temperature of the system to the room temperature, respectively extracting and washing with acetic acid and ethanol, and then recrystallizing and purifying to finally obtain the intermediate aromatic amine compound 13.
Preparation of intermediate compound 14:
this example prepares an intermediate aromatic amine compound 14, compound P formula and synthetic route as follows:
the specific reaction steps are as follows:
compared with the intermediate compound 13, the difference is that 9-fluorenone is changed into benzophenone with equivalent weight, other raw materials and steps are the same as the intermediate compound 13, and finally the intermediate aromatic amine compound 14 is obtained.
Preparation of intermediate compound 15:
this example prepares an intermediate aromatic amine compound 15, having the formula for compound P and the synthetic route as follows:
the specific reaction steps are as follows:
compared with the intermediate compound 13, the difference is that 9-fluorenone is changed into xanthone with equivalent weight, other raw materials and steps are the same as the intermediate compound 13, and finally the intermediate aromatic amine compound 15 is obtained.
Preparation of intermediate compound 16:
this example prepares an intermediate aromatic amine compound 16, having the formula for compound P and the synthetic route as follows:
the specific reaction steps are as follows:
compared with the intermediate compound 13, the difference is that 9-fluorenone is changed into thioxanthone with equivalent weight, other raw materials and steps are the same as the intermediate compound 13, and finally the intermediate aromatic amine compound 16 is obtained.
Preparation of intermediate compound 17:
this example prepares an intermediate aromatic amine compound 17, compound P formula and synthetic route as follows:
the specific reaction steps are as follows:
compared with the intermediate compound 13, the difference is that 9-fluorenone is changed into thioxanthone 10, 10-dioxide with equivalent weight, other raw materials and steps are the same as the intermediate compound 13, and finally the intermediate aromatic amine compound 17 is obtained.
Preparation of intermediate compound 18:
this example prepares an intermediate aromatic amine compound 18, compound P formula and synthetic route as follows:
the specific reaction steps are as follows:
compared with the intermediate compound 13, the difference is that 9-fluorenone is changed into 10, 10-dimethylanthrone with equivalent weight, other raw materials and steps are the same as the intermediate compound 13, and finally the intermediate aromatic amine compound 18 is obtained.
Preparation of intermediate compound 19:
this example prepares an intermediate aromatic amine compound 19, compound P formula and synthetic route as follows:
the specific reaction steps are as follows:
compared with the intermediate compound 13, the difference is that 9-fluorenone is replaced by equivalent 9, 9-Dimethyl-9-silanthracen-10 (9H) -one, other raw materials and steps are the same as the intermediate compound 13, and finally the intermediate aromatic amine compound 19 is obtained.
Preparation of intermediate compound 20:
this example prepares an intermediate aromatic amine compound 20, compound P formula and synthetic route as follows:
the specific reaction steps are as follows:
compared with the intermediate compound 13, the difference is that 9-fluorenone is changed into 9, 10-anthraquinone with equivalent weight, and other raw materials and steps are the same as the intermediate compound 13, and finally the intermediate aromatic amine compound 20 is obtained.
The preparation method of the aromatic amine compound used as the intermediate of the compounds P21-P35 of the present invention is not limited, but a typical but non-limiting synthetic route and preparation method are as follows:
wherein X is F or Br or I; r may be: 9H-carbazole; diphenylamine; 9H-bis 4-tert-butylcarbazole; bis 4-tert-butyldiphenylamine; 9H-bis 4-methoxycarbazole; 3,9' -bicarbazole; n, N-bis (phenyl) -9H-carbazol-3-amine; 3',6' -di-tert-butyl-9H-3,9' -carbazole; n, N-bis (4-tert-butyl) phenyl-9H-carbazol-3-amine; 3',6' -dimethoxy-9H-3,9' -carbazole.
If and only if only one X in a single compound of the raw material is F or Br or I; and the other is H, namely only one of 3-position and 6-position of carbazole of the starting material is substituted by halogen, and the reaction conditions are as follows: the raw material compound M (1.0eq.) and 4-methylbenzenesulfonyl chloride (1.0eq.) are subjected to protection reaction in anhydrous DMF; then carrying out Ullman reaction with a compound R (1.0eq) (R is sequentially 9H-carbazole, diphenylamine, 9H-bis-4-tert-butylcarbazole, bis-4-tert-butyldiphenylamine, 9H-bis-4-methoxycarbazole, 3,9' -bicarbazole, N-bis (phenyl) -9H-carbazole-3-amine, 3',6' -di-tert-butyl-9H-3,9' -carbazole, N-bis (4-tert-butyl) phenyl-9H-carbazole-3-amine, 3',6' -dimethoxy-9H-3,9' -carbazole) under the alkaline condition of K2CO3(2.0eq) and CuI (0.1 eq); and finally, deprotecting under a strong alkali condition, and purifying by recrystallization to obtain the aromatic amine compound (the compounds 21-30 are obtained in sequence according to the difference of the compounds R). The compounds 26-30 can be obtained by using the compounds 21-25 as the compounds R in the preparation method.
When two X in a single compound of the raw material are F, Br or I at the same time, namely 3-position and 6-position of carbazole of the starting material are simultaneously substituted by halogen atoms, the reaction conditions are as follows: the raw material compound M (1.0eq.) and 4-methylbenzenesulfonyl chloride (1.0eq.) are subjected to protection reaction in anhydrous DMF; then the reaction product and a compound R (2.0eq) (R is sequentially 9H-carbazole; diphenylamine; 9H-bis-4-tert-butylcarbazole; bis-4-tert-butyldiphenylamine; 9H-bis-4-methoxycarbazole) are subjected to Ullman reaction under the alkaline condition that K2CO3(4.0eq) and CuI (0.2eq) exist; and finally, deprotecting under a strong alkali condition, and purifying by recrystallization to obtain the aromatic amine compound (the compounds 31-35 are obtained in sequence according to the difference of the compound R).
The following are examples of the use of the compounds of the invention in organic light-emitting diode (O L ED) devices:
the stacked structure of the organic electroluminescent device used in this embodiment may be the following structure:
1. anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
2. Anode/hole injection layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
3. Anode/hole injection layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode
4. Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode
5. Anode/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/cathode
6. Anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode
7. Anode/hole transport layer/light-emitting layer// electron transport layer/cathode
8. Anode/hole transport layer/electron blocking layer/light emitting layer/cathode
9. Anode/hole transport layer/light emitting layer/cathode
10. Anode/electron blocking layer/light emitting layer/cathode
Among the above structures, the structure 3 is preferable. However, the structure of the organic electroluminescent device is not limited to the above-described examples.
The organic electroluminescent device of the electroluminescent material based on 3-benzoylpyridine as the receptor unit is obtained through a laminated structure 3, and the laminated structure is as follows:
the glass substrate/ITO/TAPC/mCP/compound light-emitting layer/TmPyPB/L iF/Al.ITO is used as an anode, TAPC is used as a hole injection layer, mCP is used as an electron blocking layer, TmPyPB is used as an electron transport layer, L iF is used as an electron injection layer, and Al is used as a cathode, wherein the compound light-emitting layer is selected from DPEPO, mCBP, CBP, CP, mCP and the like which are used as light-emitting material doping hosts besides non-doping.
The preparation steps of the light emitting device with the laminated structure are as follows:
the method comprises the steps of sequentially ultrasonically cleaning ITO transparent conductive glass by using acetone, a micron-sized detergent special for a semiconductor, deionized water and isopropanol for 15 minutes to remove dirt on the surface of the substrate, then drying the ITO transparent conductive glass in a thermostat at 80 ℃ for later use, treating the dried ITO substrate by using an oxygen plasma starting device for 3 minutes to further remove organic attachments on the surface, placing the glass with the anode ITO in a vacuum chamber under the vacuum condition of 1 × 10-5-9 × 10-3Pa to remove organic attachments on the surface, and then placing the glass with the anode ITO in the vacuum chamber
Deposition rate of (2) vapor-depositing a layer of organic material on the anodic filmWherein, in the vapor deposition of the luminescent layer, DPEPO and luminescent materials are respectively arranged on two vapor deposition sources, and the mixing ratio of the DPEPO and the luminescent materials is controlled by a certain deposition rate. Then is followed by
To evaporate L iF at a deposition rate of
The Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.
The organic electroluminescent element produced from the compound P16 of this example had CIE color coordinate values of (0.25, 0.51) and a maximum luminance of 11400cd/m2The external quantum efficiency was 23.2% and the power efficiency was 57.9 lm/W. The basic characterization data are shown in table 1. The more important advantages of the present invention are that the small molecular organic materials (compounds P15 and P33) having no nitrogen site, which are confirmed by the same compounds (compounds 15 and 33) as donors, show lower light-up voltage, higher current density, more excellent external quantum efficiency and more stable device lifetime than the small molecular organic materials (compounds BP-15 and BP-33) having 3-benzoylpyridine as acceptor core unit, and the comparative data of the performance are shown in Table 1.
The comparative materials BP-16 and BP-33 used in the application examples of the present invention have the following structures.
The materials used in the laminated structure in the application examples of the present invention are exemplified, but not limited to, the materials described.
Table 1 shows the results of the tests performed on O L ED devices
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The organic micromolecule photoelectric functional material based on 3-benzoyl pyridine as an acceptor unit is characterized by having the following structural general formula:
wherein:
r is selected from aromatic amine units shown in (1) to (35):
2. the preparation method of the organic micromolecule photoelectric functional material based on 3-benzoylpyridine as the receptor unit according to claim 1, characterized in that the organic micromolecule photoelectric functional material based on 3-benzoylpyridine as the receptor unit is prepared by subjecting a receptor nucleus precursor and an aromatic amine intermediate to Ullmann coupling reaction under the condition of copper catalyst and alkalinity; the receptor nuclear precursor has the following structure:
3. the preparation method of the organic small-molecule photoelectric functional material based on 3-benzoylpyridine as an acceptor unit according to claim 1, comprising the following steps:
sequentially adding (6-bromopyridine-3-yl) (phenyl) ketone, an intermediate, cuprous iodide, 1, 10-phenanthroline and anhydrous sodium carbonate into a reaction bottle, pumping nitrogen for multiple times, adding p-xylene, carrying out reflux reaction under the nitrogen condition, after the reaction is finished, recovering the system to room temperature, extracting and washing with dichloromethane and saturated saline solution, recovering an organic phase, drying with anhydrous magnesium sulfate, carrying out reduced pressure distillation to remove a solvent, and then separating and purifying a crude product by column chromatography to obtain a final product;
the intermediate is one of the following compounds:
carbazole, diphenylamine, phenoxazine, phenothiazine, 10H-phenothiazine 5, 5-dioxide, 9-dimethyl-9, 10-dihydroacridine, 10-dimethyl-5, 10-dihydrodibenzoazasilacycle, acridine-9-10H-ketone, 3, 6-di-tert-butylcarbazole, bis (4-tert-butylphenyl) amine, 3, 6-dimethoxy-9H-carbazole, 5-phenyl-5, 10-dihydro, 10H-spiro [ acridine-9, 9' -fluorene ], 9-diphenyl-9, 10-dihydroacridine, 10H-spiro [ acridine-9, 9' -xanthene ], 10H-spiro [ acridine-9, 9' -thioxanthene ], and mixtures thereof, 10H-spiro [ acridine-9, 9' -thioxanthene ]10',10' -dioxide, 10' -dimethyl 10H, 5' -dimethyl 5' H,10H-spiro [ acridine ]9,10' dibenzo-silacycle, 10H,10' H-spiro [ acridine-9, 9' -anthracene ] -10' one, 9H-3,9' -dicarbazole, N-diphenyl-9H-carbazol-3-amine, 3',6' -di-tert-butyl-9H-3,9' -dicarbazole, N-bis (4-tert-butyl) phenyl-9H-carbazol-3-amine, 3',6' -dimethoxy-9H-3,9' -dicarbazole, 9H-3,9':3', 9' -carbazole, N-diphenyl-9H- [3,9' -dicarbazole ] -3' -amine, 3',6' -dimethoxy-9-methyl-4 ' a, 9' adihydro-9H-3, 9':3', 9' -tricarbazole, N-bis (4- (tert-butyl) phenyl) -9H- [3,9' -bicarbazol ] -3' -amine, 3',6' -dimethoxy-9-methyl-4 ', 9' -dihydro-9H-3,9', 3', 9' -tricarbazole, 9' H-9,3':6', 9' -tricarbazole, N3, N3, N6, N6-tetraphenyl-9H-carbazole-3, 6-diamine, 9'H-9,3':6', 9' -tri-tert-butylcarbazole, N3, N3, N6, N6-tetrakis (4- (tert-butyl) phenyl) -9H-carbazole-3, 6-diamine, 3',6, 6' -tetramethoxy-9'H-9,3':6', 9' -tricarbazole.
4. The method for preparing the organic small-molecule photoelectric functional material based on 3-benzoylpyridine as an acceptor unit according to claim 3, wherein the refluxing under nitrogen gas comprises:
reflux reaction is carried out for 20-24 hours at 150-180 ℃ under the condition of nitrogen.
5. The application of the organic small-molecule photoelectric functional material based on 3-benzoylpyridine as an acceptor unit as claimed in claim 1, wherein the organic small-molecule photoelectric functional material is applied to an organic photoelectric device as a light-emitting material.
6. The application of the organic micromolecule photoelectric functional material based on 3-benzoylpyridine as the receptor unit according to claim 5, wherein the organic photoelectric device comprises an exciplex light-emitting layer, and the exciplex light-emitting layer is formed by adopting the organic micromolecule photoelectric functional material based on 3-benzoylpyridine as the receptor unit and is applied to an organic sensitized light-emitting device.
7. The use of the organic small molecule photoelectric functional material based on 3-benzoylpyridine as an acceptor unit according to claim 5 or 6, wherein the organic photoelectric device comprises a transparent substrate, and an anode layer, at least one organic thin film layer and a cathode layer formed on the substrate, wherein the organic thin film layer is any one or a combination of at least two of the organic small molecule photoelectric functional materials based on 3-benzoylpyridine as an acceptor unit according to claim 1.
8. The use of the organic small molecule photoelectric functional material based on 3-benzoylpyridine as an acceptor unit according to claim 7, wherein the organic thin film layer further comprises any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer.
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