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

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

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。

A series of oligoaniline-modified mono-and bis-nuclear iron（Ⅱ） complexes were synthesized successfully,and their spectroscopic and electrochemical properties were studied.The metal-to-ligand charge-transfer transition（1MLCT） bands of the 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 that of the reported complex [Fe（TPY）2]2＋.All the complexes show multiplicate redox processes based on the [Fe（TPY）2]2＋ core and oligoaniline unit.Their electrochemical behaviors can be modulated by changing the chain length and the substituent group in the oligoaniline unit.