CN103483312A - Triarylamine thianthrene organic electronic material and preparation method thereof - Google Patents
Triarylamine thianthrene organic electronic material and preparation method thereof Download PDFInfo
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- CN103483312A CN103483312A CN201310394507.5A CN201310394507A CN103483312A CN 103483312 A CN103483312 A CN 103483312A CN 201310394507 A CN201310394507 A CN 201310394507A CN 103483312 A CN103483312 A CN 103483312A
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- FNDGQQFBSSNZKS-UHFFFAOYSA-N c(cc1)ccc1N(c1ccccc1)c1ccc2Sc3cc(N(c4ccccc4)c4ccccc4)ccc3Sc2c1 Chemical compound c(cc1)ccc1N(c1ccccc1)c1ccc2Sc3cc(N(c4ccccc4)c4ccccc4)ccc3Sc2c1 FNDGQQFBSSNZKS-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
Abstract
The invention belongs to the field of organic electronic materials, and particularly relates to a triarylamine thianthrene organic electronic material and a preparation method thereof. The structure of the functional material provided by the invention comprises thianthrene and triarylamine and has the advantages that (1) similar to benzodithiophene, the thianthrene has relatively high photoelectric conversion efficiency, but the stability of the thianthrene is better; (2) with a high melting point, the material is suitable for a vacuum evaporation process and is compatible with the existing preparation process of solar batteries. The material provided by the invention is prepared by a two-step process by taking 2,7-dibromothianthrene, phenylamine, iodine, organic iodide substitute, sodium hydroxide, sodium carbonate, CuCl and reducing copper powder as start raw materials, and the production cost is low.
Description
Technical field
The invention belongs to the organic electronic material technical field, be specifically related to a kind of three arylamine thianthrene organic electronic materials and preparation method thereof.
Background technology
Organic photoelectrical material is the organic materials that a class has photoelectric activity, is widely used in the fields such as Organic Light Emitting Diode, organic transistor, organic solar batteries, organic memory.Organic photoelectrical material normally is rich in carbon atom, has the organic molecule of large Π conjugated system, is divided into small molecules and polymkeric substance two classes.With inorganic materials, compare, organic photoelectrical material can be realized big area preparation and flexible device preparation by solution method.In addition, organic materials has diversified structure and forms and broad property regulation space, can carry out molecular designing and obtain needed performance, can carry out the device assembling mode from bottom to top such as self-assembly and prepare nano-device and molecular device.With the photoelectric transformation efficiency of inorganic silicon solar cell, compare, the light conversion efficiency of organic solar batteries still rests on lower level.Therefore, the research core of organic solar batteries is to improve the photoelectric transformation efficiency of battery.By device architecture reasonable in design, improve interface topography, improve the methods such as polymkeric substance crystallization degree, the photoelectric transformation efficiency of organic solar batteries is greatly improved.For the more effective infrared part of utilizing in sunlight.At present the research of narrow band gap polymer organic semiconductor is also started to cause people's concern, become a new focus of organic solar batteries, by adopting benzo two thiophene-based narrow band gap polymkeric substance, realized that photoelectric transformation efficiency surpasses 7% organic solar batteries.
The present invention is combined with electron-donating group three arylamine with the electron-withdrawing group thianthrene, is a kind of novel organic electronic material, and its advantage is as follows: (1) thianthrene and benzo two thiophene-based seemingly, have higher photoelectric transformation efficiency, but the stability of thianthrene are better.(2) fusing point of material reach 270 ℃ and more than, be suitable for vacuum evaporation process, with existing solar cell, to prepare processing procedure compatible mutually.(3) add three arylamine in molecular structure, to improving photoelectric transformation efficiency, there is promoter action the prolongation device transformation period.
Summary of the invention
The object of the invention is to propose class three arylamine thianthrene organic electronic materials and preparation method thereof.
The three arylamine thianthrene organic electronic materials that the present invention proposes, structurally contain thianthrene, and two three arylamine, and its structural formula is as follows:
Wherein R is a kind of of methyl, ethyl, phenyl, 4-aminomethyl phenyl, 1-naphthyl.
The following several organic electronic materials of the special proposition of the present invention:
(1) Chinese: N
2, N
7-dimethyl-N
2, N
7-phenylbenzene thianthrene-2, the 7-diamines
English name: N
2, N
7-dimethyl-N
2, N
7-diphenylthianthrene-2,7-diamine
Molecular formula is C
26h
22n
2s
2, chemical structural formula is as follows:
(2) Chinese: N
2, N
7-diethyl-N
2, N
7-phenylbenzene thianthrene-2, the 7-diamines
English name: N
2, N
7-diethyl-N
2, N
7-diphenylthianthrene-2,7-diamine
Molecular formula is C
28h
26n
2s
2, chemical structural formula is as follows:
(3) Chinese: N
2, N
2, N
7, N
7-tetraphenyl thianthrene-2, the 7-diamines
English name: N
2, N
2, N
7, N
7-tetraphenylthianthrene-2,7-diamine
Molecular formula is C
36h
26n
2s
2, chemical structural formula is as follows:
(4) Chinese: N
2, N
7-phenylbenzene-N
2, N
7-di-p-tolyl thianthrene-2, the 7-diamines
English name: N
2, N
7-diphenyl-N
2, N
7-dip-tolylthianthrene-2,7-diamine
Molecular formula is C
38h
30n
2s
2, chemical structural formula is as follows:
(5) Chinese: N
2, N
7-bis-(1-naphthyl)-N
2, N
7-phenylbenzene thianthrene-2, the 7-diamines
English name: N
2, N
7-di (naphthalen-1-yl)-N
2, N
7-diphenylthianthrene-2,7-diamine
Molecular formula is C
44h
30n
2s
2, chemical structural formula is as follows:
The invention allows for the preparation method of such organic electronic material, this material is by 2,7-dibromo thianthrene, aniline, iodine, organic iodine are starting raw material for thing, sodium hydroxide, sodium carbonate, CuCl and copper reduction, by two-step approach, prepare, and reaction equation is as follows:
Concrete steps are as follows:
Under nitrogen protection, 2,7-dibromo thianthrene, aniline, iodine are mixed; be heated to 120 ℃ of reactions 6 hours; add ethanol, filter, solid mixes for thing, sodium hydroxide, sodium carbonate, CuCl and copper reduction with organic iodine; add n-dodecane; be heated to 140～180 ℃ of reactions 12 hours, add ethanol, filter; solid is purified by the vacuum-sublimation method, obtains the target organic electronic material.
The accompanying drawing explanation
Fig. 1 is three arylamine thianthrene organic electronic material structural formulas.
Embodiment
The invention is further illustrated by the following examples
Embodiment 1
Under nitrogen protection, in three-necked bottle, by 0.01mol2; 7-dibromo thianthrene, 0.024mol aniline, 50mg iodine mix, and are heated to 120 ℃ of reactions 6 hours, add ethanol 100mL; filter; solid mixes with 0.025mol methyl iodide, 0.02mol sodium hydroxide, 0.02mol sodium carbonate, 0.02molCuCl and 0.2g copper reduction, adds n-dodecane 100mL, is heated to 140 ℃ of reactions 12 hours; add ethanol 200mL; filter, solid is purified by the vacuum-sublimation method, obtains N
2, N
7-dimethyl-N
2, N
7-phenylbenzene thianthrene-2,7-diamines (A), yield: 66%, fusing point: 270-272 ℃, ultimate analysis: C, 73.22; H, 5.22; N, 6.53; S, 15.03, calculated value C, 73.20; H, 5.20; N, 6.57; S, 15.03, mass spectrometric measurement: m/z:426 (100.0%).
Embodiment 2
Under nitrogen protection, in three-necked bottle, by 0.01mol2; 7-dibromo thianthrene, 0.024mol aniline, 50mg iodine mix, and are heated to 120 ℃ of reactions 6 hours, add ethanol 100mL; filter; solid mixes with 0.025mol iodoethane, 0.02mol sodium hydroxide, 0.02mol sodium carbonate, 0.02molCuCl and 0.2g copper reduction, adds n-dodecane 100mL, is heated to 180 ℃ of reactions 12 hours; add ethanol 200mL; filter, solid is purified by the vacuum-sublimation method, obtains N
2, N
7-diethyl-N
2, N
7-phenylbenzene thianthrene-2,7-diamines (B), yield: 63%, fusing point: 286-288 ℃, ultimate analysis: C, 73.93; H, 5.79; N, 6.18; S, 14.10, calculated value C, 73.97; H, 5.76; N, 6.16; S, 14.11, mass spectrometric measurement: m/z:454 (100.0%).
Embodiment 3
Under nitrogen protection, in three-necked bottle, by 0.01mol2; 7-dibromo thianthrene, 0.024mol aniline, 50mg iodine mix, and are heated to 120 ℃ of reactions 6 hours, add ethanol 100mL; filter; solid mixes with 0.025mol iodobenzene, 0.02mol sodium hydroxide, 0.02mol sodium carbonate, 0.02molCuCl and 0.2g copper reduction, adds n-dodecane 100mL, is heated to 160 ℃ of reactions 12 hours; add ethanol 200mL; filter, solid is purified by the vacuum-sublimation method, obtains N
2, N
2, N
7, N
7-tetraphenyl thianthrene-2,7-diamines (C), yield: 42%, fusing point: 300 ℃, ultimate analysis: C, 78.50; H, 4.74; N, 5.09; S, 11.67, calculated value C, 78.51; H, 4.76; N, 5.09; S, 11.64, mass spectrometric measurement: m/z:550 (100.0%).
Embodiment 4
Under nitrogen protection, in three-necked bottle, by 0.01mol2; 7-dibromo thianthrene, 0.024mol aniline, 50mg iodine mix, and are heated to 120 ℃ of reactions 6 hours, add ethanol 100mL; filter; solid mixes with 0.025mol4-methyl iodobenzene, 0.02mol sodium hydroxide, 0.02mol sodium carbonate, 0.02molCuCl and 0.2g copper reduction, adds n-dodecane 100mL, is heated to 180 ℃ of reactions 12 hours; add ethanol 200mL; filter, solid is purified by the vacuum-sublimation method, obtains N
2, N
7-phenylbenzene-N
2, N
7-di-p-tolyl thianthrene-2,7-diamines (D), yield: 45%, fusing point: 300 ℃, ultimate analysis: C, 78.83; H, 5.20; N, 4.87; S, 11.10, calculated value C, 78.86; H, 5.22; N, 4.84; S, 11.08, mass spectrometric measurement: m/z:578 (100.0%).
Embodiment 5
Under nitrogen protection, in three-necked bottle, by 0.01mol2, 7-dibromo thianthrene, 0.024mol aniline, 50mg iodine mixes, be heated to 120 ℃ of reactions 6 hours, add ethanol 100mL, filter, solid and 0.025mol1-naphthalene iodide, 0.02mol sodium hydroxide, 0.02mol sodium carbonate, 0.02molCuCl and the 0.2g copper reduction mixes, add n-dodecane 100mL, be heated to 160 ℃ of reactions 12 hours, add ethanol 200mL, filter, solid is purified by the vacuum-sublimation method, obtain N2, N7-bis-(1-naphthyl)-N2, N7-phenylbenzene thianthrene-2, 7-diamines (E), yield: 26%, fusing point: > 300 ℃, ultimate analysis: C, 81.22, H, 4.63, N, 4.33, S, 9.82, calculated value C, 81.20, H, 4.65, N, 4.30, S, 9.85, mass spectrometric measurement: m/z:650 (100.0%).
Claims (7)
1. arylamine thianthrene organic electronic material and preparation method thereof, is characterized in that this material structurally contains thianthrene, and two three arylamine, and its structural formula is as follows:
Wherein R is a kind of of methyl, ethyl, phenyl, 4-aminomethyl phenyl, 1-naphthyl.
2. organic electronic material according to claim 1, is characterized in that R is methyl, and the molecular formula of material is C
26h
22n
2s
2, chemical structural formula is as follows:
The name of this compound is called: N
2, N
7-dimethyl-N
2, N
7-phenylbenzene thianthrene-2, the 7-diamines
English name is: N
2, N
7-dimethyl-N
2, N
7-diphenylthianthrene-2,7-diamine.
3. organic electronic material according to claim 1, is characterized in that R is ethyl, and the molecular formula of material is C
28h
26n
2s
2, chemical structural formula is as follows:
The name of this compound is called: N
2, N
7-diethyl-N
2, N
7-phenylbenzene thianthrene-2, the 7-diamines
English name is: N
2, N
7-diethyl-N
2, N
7-diphenylthianthrene-2,7-diamine.
4. organic electronic material according to claim 1, is characterized in that R is phenyl, and the molecular formula of material is C
36h
26n
2s
2, chemical structural formula is as follows:
The name of this compound is called: N
2, N
2, N
7, N
7-tetraphenyl thianthrene-2, the 7-diamines
English name is: N
2, N
2, N
7, N
7-tetraphenylthianthrene-2,7-diamine.
5. organic electronic material according to claim 1, is characterized in that R is the 4-aminomethyl phenyl, and the molecular formula of material is C
38h
30n
2s
2, chemical structural formula is as follows:
The name of this compound is called: N
2, N
7-phenylbenzene-N
2, N
7-di-p-tolyl thianthrene-2, the 7-diamines
English name is: N
2, N
7-diphenyl-N
2, N
7-dip-tolylthianthrene-2,7-diamine.
6. organic electronic material according to claim 1, is characterized in that R is the 1-naphthyl, and the molecular formula of material is C
44h
30n
2s
2, chemical structural formula is as follows:
The name of this compound is called: N
2, N
7-bis-(1-naphthyl)-N
2, N
7-phenylbenzene thianthrene-2, the 7-diamines
English name is: N
2, N
7-di (naphthalen-1-yl)-N
2, N
7-diphenylthianthrene-2,7-diamine.
7. the preparation method as the described organic electronic material of claim 1～6, it is characterized in that this material is by 2,7-dibromo thianthrene, aniline, iodine, organic iodine are starting raw material for thing, sodium hydroxide, sodium carbonate, CuCl and copper reduction, by two-step approach, prepare, reaction equation is as follows:
Concrete steps are as follows:
Under nitrogen protection, 2,7-dibromo thianthrene, aniline, iodine are mixed; be heated to 120 ℃ of reactions 6 hours; add ethanol, filter, solid mixes for thing, sodium hydroxide, sodium carbonate, CuCl and copper reduction with organic iodine; add n-dodecane; be heated to 140～180 ℃ of reactions 12 hours, add ethanol, filter; solid is purified by the vacuum-sublimation method, obtains the target organic electronic material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732574A (en) * | 2016-03-24 | 2016-07-06 | 中国科学院理化技术研究所 | Preparation method of thianthrene-5,5,10,10-tetroxide derivative and organic electroluminescence device based on thianthrene-5,5,10,10-tetroxide derivative |
| KR101863942B1 (en) * | 2015-08-28 | 2018-07-06 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
| CN109312023A (en) * | 2016-08-05 | 2019-02-05 | 赢创德固赛有限公司 | Contain purposes of the polymer as charge storage of thianthrene |
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| US4931371A (en) * | 1987-11-24 | 1990-06-05 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member |
| CN1918141A (en) * | 2004-02-09 | 2007-02-21 | 新日铁化学株式会社 | Aminodibenzodioxin derivative and organic electroluminescent device using same |
| CN101233127A (en) * | 2005-08-03 | 2008-07-30 | 新日铁化学株式会社 | Heterocyclic compound and organic electroluminescent device using same |
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2013
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Patent Citations (3)
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|---|---|---|---|---|
| US4931371A (en) * | 1987-11-24 | 1990-06-05 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member |
| CN1918141A (en) * | 2004-02-09 | 2007-02-21 | 新日铁化学株式会社 | Aminodibenzodioxin derivative and organic electroluminescent device using same |
| CN101233127A (en) * | 2005-08-03 | 2008-07-30 | 新日铁化学株式会社 | Heterocyclic compound and organic electroluminescent device using same |
Non-Patent Citations (1)
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|---|
| IANI S. PERETEANU ET AL.: "Synthesis and electronic properties of 3,7-dianilino substituted N-hexyl phenothiazines", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101863942B1 (en) * | 2015-08-28 | 2018-07-06 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
| US10361373B2 (en) | 2015-08-28 | 2019-07-23 | Samsung Display Co., Ltd. | Condensed-cyclic compound and organic light emitting device comprising the same |
| CN105732574A (en) * | 2016-03-24 | 2016-07-06 | 中国科学院理化技术研究所 | Preparation method of thianthrene-5,5,10,10-tetroxide derivative and organic electroluminescence device based on thianthrene-5,5,10,10-tetroxide derivative |
| CN105732574B (en) * | 2016-03-24 | 2019-03-05 | 中国科学院理化技术研究所 | The preparation of thianthrene -5,5,10,10- tetroxide derivative and the organic electroluminescence device based on it |
| CN109312023A (en) * | 2016-08-05 | 2019-02-05 | 赢创德固赛有限公司 | Contain purposes of the polymer as charge storage of thianthrene |
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Application publication date: 20140101 |