二茂铁与HnXW12O40.mH2O(X=P,Si, Ge)电荷转移配合物的室温固相合 成与性质

用室温固相反应法合成了三种具有非线性光学性质的二茂铁-多金属氧酸盐电荷转移配合物Fe(C5H5)2H]3PW12O40(Ⅰ)，Fe(C5H5)2H]4SiW12O40(Ⅱ)和Fe(C5H5)2H]4GeW12O40(Ⅲ)。用元素分析、紫外漫反射电子光谱、红外光谱、穆斯堡尔谱、ESR、XRD、循环伏安等手段对其进行了表征和研究，确定了该配合物的组成与结构，结果表明二茂铁与杂多阴离子之间发生了电荷转移，在形成配合物过程中杂多阴离子发生单电子还原反应，生成了混合价化合物，非线性光学性质研究表明电荷转移配合物的倍频效应强度分别为IⅠ^2ω=0.27I~KDP,IⅡ^2ω=0.06I~KDP,IⅢ^2ω=0.10I~KDP;三阶非线性光学χⅠ^(3)=2.4×10^-^13esu,χⅡ^(3)=3.1×10^-^12esu,χⅢ^(3)=6.5×10^-^12esu.

Solid state synthesis, characterization and physical properties of charge-transfer complexes based on ferrocene and HnXW12O40.mH2O(X=P, Si, Ge) at room temperature

The charge transfer complexes, Fe(C5H5)2H]3PW12O40(Ⅰ)， Fe(C5H5) 2H]4SiW12O40(Ⅱ) and Fe(C5H5)2H]4GeW12O40(Ⅲ), have been synthesized from organic donor ferrocene Fe(C5H5)2] and inorganic acceptor Keggin structure HnXW12O40.mH2O(X=P, Si, Ge) by one step solid state reaction at room temperature and characterized by elemental analysis, reflectance spectroscopy, FT-IR, XRD, ESR measurements, Mossbauer spectra and CV. The results indicate that the anions of the heteropoly acids remain unchanged in the charge tranfer complexes formation. The nonlinear optical property measurements indicate the second harmonic generation intensity of the three charge transfer complexes: IⅠ^2ω=0.27I~KDP, IⅡ^2ω=0.06 I~KDP, IⅢ^2ω=0.10 I~KDP, and the third-order susceptibility is χⅠ^(3)=2.4×10^-^13 esu, χⅡ^(3)=3.1×10^-^12 esu, χⅢ^(3)=6.5×10^-^12 esu.