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有机化学
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有机化学 ›› 2011, Vol. 31 ›› Issue (11): 1842-1847. 上一篇    下一篇

研究论文

基于喹啉与苯胺衍生物不对称方酸菁染料的合成与光谱性质

王振宇，傅南雁*   

  1. (福州大学化学化工学院 福建省光催化重点实验室-省部共建国家重点实验室培育基地 福州 350002)
  • 收稿日期:2011-01-17 修回日期:2011-05-14 发布日期:2011-06-15

Synthesis and Spectral Properties of Some Unsymmetrical Squaraine Dyes Based on Quinoline and Aniline Derivatives

WANG Zhen-Yu, FU Nan-Yan   

  1. (Fujian Provincial Key Laboratory of Photocatalysis-State Key Laboratory and Breeding Base Co-developed by Province and Ministry, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350002)
  • Received:2011-01-17 Revised:2011-05-14 Published:2011-06-15

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1153

被引次数

8

设计合成了四个基于喹啉与苯胺衍生物的不对称方酸菁染料7a～7d, 利用1H NMR, MS和元素分析对结构进行了表征. 对中间体碘盐3a～3c的合成条件进行了探索, 发现随着喹啉6位取代基吸电子能力的增强, 亲核取代反应的活性降低, 因此需要较为苛刻的条件. 对不对称方酸菁的合成方法进行了系统研究, 发现不对称方酸菁前体的接入方式是反应成败的关键, 并对该不对称方酸菁的吸收光谱与光稳定性进行了系统研究. 研究表明, 染料的吸收半峰宽较宽, 最大吸收随着溶剂极性的增加发生蓝移, 表现为负溶剂化效应. 光稳定性实验表明, 染料的光稳定较好, 且喹啉半体6位取代基吸电子能力的增加有利于染料光稳定性的增加. 此外, 苯胺半体氮上烷基链的长度对染料的光稳定性也有影响.

关键词: 不对称方酸菁, 合成, 光稳定性, 本体异质结

Four unsymmetrical squaraine dyes 7a～7d based on quinoline and aniline derivatives have been synthesized and characterized by 1H NMR, MS and elemental analysis. The synthetic conditions of the intermediates 3a～3c were investigated. As the electron withdrawing ability of the 6-position substituent of quinoline increased, the reactivity of nucleophilic substitution decreased, so the harsher condition was needed. The synthetic methods of the unsymmetrical dyes were explored. The results showed that the inoculation sequence of the precursor of unsymmetrical squaraine dyes was the key to the completion of the reaction successfully. The absorption spectra and photostability of the unsymmetrical squaraines were studied systematically. The results revealed that the half-peak width for the absorption band of the dyes was wide and the absorption spectra exhibited blue-shift with the increase of solvent polarity, showing a negative solvatochromism. The absorption decay under irra-diation demonstrated that the photostabilities of all the four dyes were high and their photostabilities en-hanced further as the electron withdrawing ability of the 6-position substituent of quinoline moiety in-creased. In addition, the length of the alkyl chain at the nitrogen of the aniline moiety also influenced the photostabilities of the dyes.

Key words: unsymmetrical squaraine, synthesis, photostability, bulk-heterojunction