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.
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