通过水热法合成了两个新型的钨氧簇化合物, {(H2Biim)2}［SiW12O40］·8H2O (1)和{Ni2(Biim)5}［SiW12O40］·4H2O (2)。 两个化合物均以经典Keggin结构簇阴离子为构筑模块形成, 化合物1属于四方晶系, 抗衡阳离子是双质子化的(H2Biim)2+, 化合物2属于单斜晶系, 以双核的［Ni2(Biim)5］4+配合物作为抗衡阳离子, 且其中心金属离子为五配位模式。 利用X射线粉末衍射、 红外光谱、 热微扰下的二维红外相关光谱和固体紫外可见漫反射光谱等方法对化合物进行研究, 探讨化合物结构与性能的关系。 红外光谱表明, 在1 050～700 cm-1, 化合物出现了典型的Keggin簇阴离子骨架吸收峰, 二维红外相关光谱进一步显示该簇阴离子骨架对热响应很敏感; 固体紫外可见漫反射光谱表明, 两个化合物分别在254和251 nm处出现了Oμ→W的LMCT跃迁。

Two novel polyoxotungstates {(H2Biim)2}［SiW12O40］·8H2O (1) and {Ni2(Biim)5}［SiW12O40］·4H2O (2) have been hydrothermally synthesized. The two compounds are formed by classic Keggin configuration cluster anions as building blocks. The compound 1 belongs to the tetragonal system with protonated (H2Biim)2+ as counter cation, while compound 2 belongs to the monoclinic system, with dual-core ［Ni2(Biim)5］4+ complex as a counter cation of which the Ni2＋ ion is five-coordinated. The relationship between their properties and structures were studied by using XRD, FTIR, two-dimensional (2D) correlation infrared spectroscopy under thermal perturbation, and Uv-Vis DRS spectrum ect. Infrared spectra showed that the stretching vibration of Keggin cluster anion skeleton appeared in the range of 1 050～700 cm-1, furthermore the two-dimensional infrared correlation spectroscopy illustrated that the anion cluster skeleton is very sensitive with the thermal response; UV-Vis DRS found the Oμ→W(LMCT) of the two compounds was in 254 and 251 nm respectively.