中华医学超声杂志

应用化学 ›› 2009, Vol. 26 ›› Issue (12): 1377-1385.

• 研究论文 •    下一篇

齐聚苯胺修饰的三联吡啶铁配合物的合成及其光谱和电化学性质

邱东方1,2,程延祥1*,王利祥1*   

  1. (1.中国科学院长春应用化学研究所高分子物理与化学国家重点实验室 长春 130022；2.中国科学院研究生院 北京)
  • 收稿日期:2008-11-20 修回日期:2009-02-17 出版日期:2009-12-10 发布日期:2009-12-10
  • 通讯作者: 程延祥，博士，研究员; E-mail:yanxiang@ciac.jl.cn; 研究方向：高分子及金属有机化学
  • 基金资助:
    国家自然科学基金（50673088和20874098）资助项目

Oligoaniline-Modified Terpyridine Iron(II) Complexes: Synthesis, Spectroscopic Property and Redox Behavior

QIU Dong-Fang1,2, CHENG Yan-Xiang1*, WANG Li-Xiang1*   

  1. (1.State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of
    Applied Chemistry,Chinese Academy of Sciences,Changchun 130022;
    2.Graduate School of the Chinese Academy of Sciences,Beijing)
  • Received:2008-11-20 Revised:2009-02-17 Published:2009-12-10 Online:2009-12-10

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摘要：

合成了一系列齐聚苯胺修饰的三联吡啶铁配合物，研究了齐聚苯胺链长、不同取代基等对配合物光谱性质和氧化还原性质的影响。 结果表明，相对于配合物[Fe(TPY)2]2+(TPY:三联吡啶)，供电子齐聚苯胺单元的引入，使得修饰基团与配合物中心核[Fe(TPY)2]2+之间形成了强的D-A体系，导致配合物1MLCT吸收波长显著红移至594 nm，且摩尔吸光系数增加近5倍。 配合物同时具有基于金属中心、三联吡啶配体和齐聚苯胺单元的多个氧化还原过程，强拉电子取代基使齐聚苯胺单元氧化还原峰简并且峰电势明显正移，而正丁基取代基对氧化还原峰电势的影响较小。

关键词: 三联吡啶, 铁, 齐聚苯胺, 吸收光谱, 电化学

Abstract:

A series of oligoaniline-modified mono- and bis-nuclear iron(II) complexes have been synthesized successfully, and their spectroscopic and electrochemical properties have been studied. The metal-to-ligand charge-transfer transition (1MLCT) bands of complexes with oligoaniline groups are considerably red-shifted (converge to 594 nm with increasing chain length) and their intensities become much more intense (approximately 5 times), compared with those of the reported complex [Fe(TPY)2]2+. All complexes show multiplicate redox processes based on the [Fe(TPY)2]2+ core and oligoaniline unit. Their electrochemical behavior can be modulated by changing the chain length and the substituented group in oligoaniline unit.

Key words: terpyridine, iron, oligoaniline, spectroscopy, electrochemistry

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