乙酰二茂铁缩肼基硫代甲酸苄酯镍/钴配合物现场红外光谱电化学研究

本文对非线性光学材料乙酰二茂铁缩肼基硫代甲酸苄酯 (HLSB)的镍 /钴配合物Ni(LSB) 2 /Co(LSB) 2进行了电化学和现场红外光谱电化学的比较研究 ,结果表明 ,平面型镍配合物桥联双二茂铁体系中的电子离域程度高 ,其氧化分为两步单电子可逆过程 ,分子内的两个二茂铁基之间存在着较强的电子交流 ,电子传递主要是通过配体的骨架链进行的 ,观察到出现在 1 4 53cm- 1 处的νCC 伸缩强振动峰。而变形四面体钴配合物桥联双二茂铁体系的氧化为一步两电子过程 ,分子中的电子离域程度低 ,抑制了两个二茂铁基之间的电子交流 ,两个二茂铁基近乎等同。

Study on S-benzyl-N-(ferrocenyl-1-methyl-metylidene)-Dithiocarbazate Nickel(Ⅱ)/Cobalt(Ⅱ) Complexes by In-situ FTIR Spectroelectrochemistry

Comparative studies were carried out by using electrochemistry and in-situ FTIR spectroelectrochemistry for nonlinear optical complexes, S-benzyl-N-(ferrocenyl-1-methyl-metylidene)-dithiocarbazate nickel (II)/cobalt (II) complexes (Ni(LSB)2/Co (LSB)2). The results indicated that Ni(LSB)2 involves two consecutive reversible one-electron oxidation steps, while Co(LSB)2 involves only one two-electron oxidation step. Ni(LSB)2 complex that has a square planar configuration exhibits a moderately strong electronic communication between the two-ferrocene moieties, taking place through the skeleton chain of the ligand due to the extensive electron delocalization in the whole molecule and leads to the appearance of a strong nu c-c vibration band at 1,453 cm-1 during the oxidation process, while Co(LSB)2 complex that has a tetrahedral configuration shows low electron delocalization and has two almost identical ferrocene moieties.