电荷转移盐[Fe(Cp)_2]_4[HSiMo^VMo_(11)^(VI)O_(40)]·2CH_3CN·H_2O的合成、晶体结构及谱学表征

Synthesis,crystal structure and spectroscopy characterization of a charge-transfer salt [Fe(Cp)_2]_4[HSiMo^VMo_(11)^(VI)O_(40)]·2CH_3CN·H_2O

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2.90~3.21A;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 new charge-transfer salt [Fe( Cp)2]4[HSiMoVMoVI11O40]·2CH3CN·H2O was synthesized by the reaction of ferrocene with Keggin-type( Bu4N)4[SiMo12O40]in acetonitrile solution,and high yield rate is obtained. The crystal structural analysis reveals that each reduced Keggin polyanion is surrounded by nine [Fe( Cp)2]+ cations and they interact each other by coulomb force,and the distance between framework oxygens of Keggin anion and carbon atoms of [Fe( Cp)2]+is 2. 90 ~ 3. 21 A; [Fe( Cp)2]+moieties are stacked to form one-dimentional chains along [011] direction by strong π…π interactions. The diffuse reflectance spectrum( DRS) of the title compound in the solid state presents a new strong absorption peak extending up to λmax = 620 nm,which ascribes to the charge transfer process between the ferrocene donor and the polyanion acceptor. The FTIR,fluorescence spectra( FS) and cyclic voltammetry( CV) spectrum characterizations of the title compound are also discussed.