研究论文

含三苯胺基团的二噻吩乙烯光致变色化合物的合成及性能研究

  • 王志强 ,
  • 肖殷 ,
  • 金会义 ,
  • 谈廷风 ,
  • 王世荣 ,
  • 李祥高
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  • a. 天津大学化工学院 天津 300072;
    b. 天津化学化工协同创新中心 天津 300072;
    c. 天津城建大学理学院 天津 300384

收稿日期: 2014-03-07

  网络出版日期: 2014-05-14

基金资助

项目受国家自然科学基金(No.21102098)和国家高技术研究发展计划(863计划,No.2012AA030307)资助.

Synthesis and Properties of Photochromic Dithienylethene Compounds with Triphenylamine Units

  • Wang Zhiqiang ,
  • Xiao Yin ,
  • Jin Huiyi ,
  • Tan Tingfeng ,
  • Wang Shirong ,
  • Li Xianggao
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  • a. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072;
    b. The Co-Innovation Center of Chemistry and Chemical Engineering of Tianjin, Tianjin 300072;
    c. School of Science, Tianjin Chengjian University, Tianjin 300384

Received date: 2014-03-07

  Online published: 2014-05-14

Supported by

Project supported by the National Natural Science Foundation of China (No.21102098) and the National High Technology Research and Development Program of China (863 Program, No.2012AA030307).

摘要

以5-氯-2-甲基-3-乙酰基噻吩和二苯氨基苯甲醛为原料,经Aldol反应、Michael反应及McMurry反应,将光致变色单元和三苯胺基团结合起来,合成了三种二噻吩乙烯类光致变色化合物1a1c,并通过MS,1H NMR和13C NMR对其结构进行了表征.与以往主要从两侧噻吩环引入不同功能性基团的研究不同,本文将具有荧光性的三苯胺基团通过单键桥连至环戊烯β位上,在保持光致变色反应活性的同时,也避免其它功能性基团对二噻吩乙烯骨架的影响.通过紫外-可见吸收光谱和荧光光谱研究了其在溶液及聚甲基丙烯酸甲酯薄膜中的光致变色性能和荧光性能.在302 nm紫外光照射下,1a1c的溶液和薄膜由无色变为黄色,并能快速达到光稳态;用450 nm蓝光照射时,能在较短时间内恢复至无色.在紫外光的激发下,1a1c的最大荧光发射波长随着取代基R供电子效应的增强而增大;1a1c在正己烷、甲苯和乙酸乙酯中具有较强的荧光,在乙腈中荧光较弱,而在氯仿中几乎没有荧光.在302 nm紫外光照射下,1a1c的三苯胺基团和二噻吩环戊烯基团之间发生荧光共振能量转移,其荧光强度随着光照时间的延长逐渐降低,表明其具有作为荧光分子开关的潜力.

本文引用格式

王志强 , 肖殷 , 金会义 , 谈廷风 , 王世荣 , 李祥高 . 含三苯胺基团的二噻吩乙烯光致变色化合物的合成及性能研究[J]. 化学学报, 2014 , 72(6) : 731 -738 . DOI: 10.6023/A14030158

Abstract

Combining dithienylethene photochromic unit with triphenylamine unit, three new photochromic dithienylethene compounds 1a1c were successfully synthesized using 5-chloro-2-methyl-3-acetylthiophene and diphenylaminobenzaldehydes as starting materials through Aldol condensation reaction, Michael addition reaction and McMurry coupling reaction, the structures of which were characterized by MS, 1H NMR and 13C NMR.Different from majority of previous studies that introduce different functional groups through thiophene rings, we bridged the triphenylamine unit with fluorescence property to the cyclopentene at β-position via C—C single bond, which will maintain the activation of photochromism and prevent other functional groups affecting the dithienylethene backbone.Their photochromic and fluorescence properties in solutions and polymethylmethacrylate films were investigated by UV-Vis and fluorescence spectra, respectively.The colorless solutions and films of 1a1c switch to yellow upon irradiation with 302 nm UV light and reach the photostationary state fast, while bleaching of the colored solutions happen upon irradiation with 450 nm blue light.When 1a1c are excited by UV light, the maximum fluorescence wavelengths of 1a1c increase along with the enhancement of the abilities of electron donating of substituent R, and 1a1c emit strong fluorescence in n-hexane, toluene and ethyl acetate, while weak in acetonitrile and none in chloroform.Moreover, upon irradiation at 302 nm, Förster resonance energy transfer occurs between triphenylamine unit and dithienylcyclopentene unit of 1a1c.Thus, the fluorescence intensities of 1a1c decrease along with the prolonging of irradiation time, which indicates the potential application of these compounds as fluorescence molecular switches.

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