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在乙腈溶液中二茂铁与(Bu4N)4[SiMo12O40]反应高产率地合成了一种新的电荷转移盐[Fe(Cp)2]4[HSiMoVMoVI11O40]·2CH3CN·H2O。单晶结构分析表明,每个单电子还原的Keggin阴离子与相邻的9个[Fe(Cp)2]+近距离地通过静电引力相互作用,Keggin阴离子骨架氧原子与二茂铁中茂环的碳原子间的距离在2.90~3.21A;在[011]方向相邻的[Fe(Cp)2]+形成一维链,链内相邻的相互平行的茂环之间存在着强的π…π堆积作用。固态漫反射光谱在620 nm附近呈现了一个新的强吸收峰,归属于二茂铁阳离子给体与杂多阴离子受体之间的电荷转移。对该电荷转移盐的红外、紫外、荧光、循环伏安等谱学性质进行了讨论。
A novel charge-transfer salt [Fe (Cp) 2] 4 [HSiMoVMoVI11O40] · 2CH3CN · H2O was synthesized with high yield of ferrocene and (Bu4N) 4 [SiMo12O40] in acetonitrile solution. Single crystal structure analysis shows that each single electron-reduced Keggin anion interacts closely with the adjacent nine [Fe (Cp) 2] + through electrostatic attraction, and the Keggin anion skeleton oxygen atoms react with the ring of the metallocene The distance between carbon atoms ranges from 2.90 to 3.21 A. [Fe (Cp) 2] + adjacent in the [011] direction forms a one-dimensional chain, and there is a strong π between the adjacent parallel rings in the chain ... π stacking effect. The solid-state diffuse reflectance spectrum exhibits a new strong absorption near 620 nm, which is attributed to the charge transfer between the ferrocene cation donor and the heteropolyanion acceptor. The IR, UV, fluorescence, cyclic voltammetric and other spectroscopic properties of the charge-transfer salt were discussed.