一种以环戊并双噻吩作为π电子桥的新型发色团的合成和电光性质的表征

doi:10.7517/j.issn.1674-0475.2015.04.300

影像科学与光化学 ›› 2015, Vol. 33 ›› Issue (4): 300-306.DOI: 10.7517/j.issn.1674-0475.2015.04.300

一种以环戊并双噻吩作为π电子桥的新型发色团的合成和电光性质的表征

杨丹^1,2, 徐化君^1,2, 丛晟宇^1,2, 薄淑晖¹, 邱玲¹, 甄珍¹, 刘新厚¹

1. 中国科学院理化技术研究所, 北京 100190;
2. 中国科学院大学, 北京 100049

收稿日期:2015-03-28 修回日期:2015-04-28 出版日期:2015-07-16 发布日期:2015-07-16
通讯作者: 刘新厚

Synthesis and Electro-optical Properties of a Novel Nonlinear Optical Chromophore Containing 4, 4-dihexyl-4H-cyclopenta [2,1-b:3,4-b'] dithiophene as π Bridge

YANG Dan^1,2, XU Huajun^1,2, CONG Shengyu^1,2, BO Shuhui¹, QIU Ling¹, ZHEN Zhen¹, LIU Xinhou¹

1. Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China;
2. University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Received:2015-03-28 Revised:2015-04-28 Online:2015-07-16 Published:2015-07-16

摘要/Abstract

摘要：

本文以4,4-二己基-4H-环戊并[2,1-b:3,4-b']二噻吩为π电子桥,合成了一种新型非线性光学发色团,并通过紫外-可见吸收光谱、热重分析以及密度泛函理论计算等对其物理和化学性质系统地进行了表征。结果表明,4,4-二己基-4H-环戊并[2,1-b:3,4-b']二噻吩作为π电子桥能有效地提高分子内的电荷转移速率和分子的一阶超极化率。同时,侧链二己基的空间位阻效应能很好地削弱分子间静电相互作用。最后,将发色团掺杂到主体聚合物聚碳酸酯中,测试得到发色团浓度为20%的极化聚合物薄膜的电光系数r₃₃为85 pm/V。

关键词: 非线性光学材料, 发色团, 电光系数, 一阶超极化率

Abstract:

A novel second-order nonlinear optical chromophores containing 4, 4-dihexyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) as π-electron bridges was prepared, and its chemical and physical properties were systematically evaluated. UV-Vis spectra, thermal stability and density functional thoery (DFT) calculations revealed that CPDT as π-spacer can dramatically enhance intramolecular charge transfer (ICT) properties and narrow the energy gaps. And due to the hindrance of dihexyl, the chromophore showed weak dipole-dipole aggregation. As expected, the poled polymer film which was prepared by doping chromophore A into amorphous polycarbonate(APC) with 20%(mass fraction) doping density, exhibited 85 pm/V in electro-optical (EO) coefficient test.

Key words: nonlinear opticalmaterial, chromophore, eocoefficient, hyperpolarizability

杨丹, 徐化君, 丛晟宇, 薄淑晖, 邱玲, 甄珍, 刘新厚. 一种以环戊并双噻吩作为π电子桥的新型发色团的合成和电光性质的表征[J]. 影像科学与光化学, 2015, 33(4): 300-306.

YANG Dan, XU Huajun, CONG Shengyu, BO Shuhui, QIU Ling, ZHEN Zhen, LIU Xinhou. Synthesis and Electro-optical Properties of a Novel Nonlinear Optical Chromophore Containing 4, 4-dihexyl-4H-cyclopenta [2,1-b:3,4-b'] dithiophene as π Bridge[J]. Imaging Science and Photochemistry, 2015, 33(4): 300-306.

参考文献

[1] Dalton L R, Sullivan P A, Bale D H. Electricfield poled organic electro-optic materials: state of the art and future prospects [J]. Chemical Reviews, 2010, 110(1):25-55.
[2] Cho M J, Choi D H, Sullivan P A, Akelaitis A J P, Dalton L R. Recent progress in second-order nonlinear optical polymers and dendrimers [J]. Progress in Polymer Science, 2008, 33(11):1013-58.
[3] Dalton L, Benight S. Theory-guided design of organic electro-optic materials and devices [J]. Polymers, 2011, 3(3):1325-51.
[4] Muhammad S, Xu H, Janjua M R S A, Su Z, Nadeem M. Quantum chemical study of benzimidazole derivatives to tune the second-order nonlinear optical molecular switching by proton abstraction [J]. Physical Chemistry Chemical Physics, 2010, 12(18):4791-9.
[5] Wu W, Qin J, Li Z. New design strategies for second-order nonlinear optical polymers and dendrimers[J]. Polymer, 2013, 54(17):4351-82.
[6] Kim O K, Fort A, Barzoukas M, Blanchard-Desce M, Lehn J M. Nonlinear optical chromophores containing dithienothiophene as a new type of electron relay [J]. Journal Material of Chemistry, 1999, 9(9): 2227-32.
[7] Benight S J, Bale D H, Olbricht B C, Dalton L R. Organic electro-optics: understanding material structure/function relationships and device fabrication issues [J]. Journal Material of Chemistry, 2009, 19(40): 7466-75.
[8] Wu W, Xin S, Xu Z, Ye C, Qin J, Li Z. Main-chain second-order nonlinear optical polyaryleneethynylenes containing isolation chromophores: enhanced nonlinear optical properties, improved optical transparency and stability [J]. Polymer Chemistry, 2013, 4(11):3196-203.
[9] Hou J H, Park M H, Zhang S, Yao Y, Chen L M, Li J H, Yang Y. Bandgap and molecular energy level control of conjugated polymer photovoltaic materials based on benzodithiophene[J]. Macromolecules, 2008, 41(16):6012-8.
[10] Slocum D W, Gierer P L. Directed metalation reactions. 8. Directed metalation of 3-mono- and 2,5-disubstituted thiophenes [J]. The Journal of Organic Chemistry, 1976, 41(23):3668-73.
[11] Beimling P, Koßmehl G. Synthesis of benzo[1,2-b':4,5-b']dithiophene and its 4,8-dimethoxy and 4,8-dimethyl derivatives [J]. ChemischeBerichte, 1986, 119(10):3198-203.
[12] He M Q, Leslie T M, Sinicropi J A. alpha-Hydroxy ketone precursors leading to a novel class of electro-optic acceptors [J]. Chemistry of Materials, 2002, 14(5):2393-400.
[13] Barlow S, Odom S A, Lancaster K, Getmanenko Y A, Mason R, Coropceanu V, Br das J L, Marder S R. Electronic and optical properties of 4H-cyclopenta[2,1-b:3,4-b']bithiophene derivatives and their 4-heteroatom-substituted analogues: a joint theoretical and experimental comparison [J]. The Journal of Physical Chemistry B, 2010, 114(45):14397-407.
[14] Wang Z, Putta A, Mottishaw J D, Wei Q, Wang H, Sun H. Molecular origin of isomerization effects on solid state structures and optoelectronic properties: a comparative case study of isomerically pure dicyanomethylene substituted fused dithiophenes [J]. The Journal of Physical Chemistry C, 2013, 117(33):16759-68.
[15] Li R, Liu J, Cai N, Zhang M, Wang P. Synchronously reduced surface states, charge recombination, and light absorption length for high-performance organic dye-sensitized solar cells [J]. The Journal of Physical Chemistry B, 2010, 114(13): 4461-4.
[16] Padhy H, Sahu D, Patra D, Pola M K, Huang J H, Chu C W, Wei K H, Lin H C. Synthesis and applications of cyano-vinylene-based polymers containing cyclopentadithiophene and dithienosilole units for photovoltaic cells [J]. Journal of Polymer Science, Part A, Polymer Chemistry, 2011, 49(15): 3417-25.
[17] Thelakkat M, Fink R, Haubner F, Schmidt H W. Synthesis and properties of novel hole transport materials for electroluminescent devices [J]. Macromolecular Symposia, 1998, 125(1): 157-64.
[18] Dickson R M, Becke A D. Basis-set-free local density-functional calculations of geometries of polyatomic-molecules[J]. Journal of Chemical Physics, 1993, 99(5):3898-905.
[19] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, et al. Gaussian 03, revision B. 03. Gaussian Inc, Pittsburgh, PA. 2003.
[20] Lee C, Parr R G. Exchange-correlation functional for atmos and molecules [J]. Physical Review A, 1990, 42(1):193-200.
[21] Yang Y H, Xu H J, Liu F G, Wang H R, Deng G W, Si P, Huang H Y, Bo S H, Liu J L, Qiu L, Zhen Z, Liu X H. Synthesis and optical nonlinear property of Y-type chromophores based on double-donor structures with excellent electro-optic activity[J]. Journal of Materials Chemistry C, 2014, 2(26):5124.
[22] Teng C C, Man H T. Simple reflection technique for measuring the electro-optic coefficient of poled polymers [J]. Applied Physics Letters, 1990, 56(18):1734.

一种以环戊并双噻吩作为π电子桥的新型发色团的合成和电光性质的表征

Synthesis and Electro-optical Properties of a Novel Nonlinear Optical Chromophore Containing 4, 4-dihexyl-4H-cyclopenta [2,1-b:3,4-b'] dithiophene as π Bridge

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 11

编辑推荐

Metrics

本文评价

[1]	邓国伟, 陈卓, 薄淑晖, 吴杰云, 黄鹤燕, 邱玲, 甄珍, 刘新厚. 基于氢键的侧链型超分子电光聚合物的制备与表征[J]. 影像科学与光化学, 2016, 34(2): 166-171.
[2]	吴峥, 薄淑晖, 肖红艳, 邱玲, 刘新厚, 甄珍. 利用β-环糊精-发色团分子超分子包合物减弱非线性发色团分子间静电相互作用的新方法[J]. 影像科学与光化学, 2010, 28(5): 321-327.
[3]	赵文轲, 王志鹏, 陈卓, 徐光明, 韩旭, 邱玲, 甄珍, 刘新厚. 一种新型的交联极化聚合物的合成及性能研究[J]. 影像科学与光化学, 2007, 25(6): 452-458.
[4]	王志鹏, 薄淑晖, 赵文轲, 刘家磊, 王建设, 邱玲, 甄珍, 刘新厚. 高热稳定性和可逆交联性质的含新型偶氮发色团电光聚合物的研究[J]. 影像科学与光化学, 2007, 25(5): 327-332.
[5]	何元君, 张镇平, 苏建华, 田禾. 三元若丹明激光染料荧光寿命研究[J]. 影像科学与光化学, 2000, 18(2): 174-178.
[6]	郭丰启, 王夺元. 不对称五氮齿镉和铟大环配合物的激发态性能研究[J]. 影像科学与光化学, 1999, 17(3): 232-238.
[7]	佟振合, 苏宁, 吴骊珠, 苑振宇. 沸石的包结作用提高分子内萘蒽的交叉光加成[J]. 影像科学与光化学, 1998, 16(2): 111-116.
[8]	籍海峰, 佟振合. 1,3-二β-萘甲酰基杯[4]芳烃的荧光光谱与光二聚反应[J]. 影像科学与光化学, 1996, 14(4): 289-292.
[9]	田禾, 苏建华, 陈孔常, 张镇平, 郭孟鑫. 新型双发色团染料荧光光谱及其寿命的研究[J]. 影像科学与光化学, 1996, 14(4): 355-359.
[10]	杨国强, 吴世康. 溶致变色法测定吡唑啉类化合物的分子二阶极化率[J]. 影像科学与光化学, 1992, 10(2): 174-179.
[11]	傅兴发, 朱紫瑜, 秦利, 沈玉全. 偶氮化合物的电晕极化薄膜及其非线性光学性能研究[J]. 影像科学与光化学, 1991, 9(3): 209-211.