电荷转移配合物(C_7H_(10)NO)_3[PW_(12)O_(40)]·6H_2O的合成、性质及晶体结构

Synthesis,Properties and Crystal Structure of a Novel Charge-Transfer Complex:(C_7H_(10)NO)_3[PW_(12)O_(40)]6H_2O

以十二钨磷酸和对甲氨基苯酚硫酸盐为原料合成了组成为(C7H10NO)3[PW12O40].6H2O的新型电荷转移配合物,通过元素分析、红外光谱、溶液紫外-可见光谱、固体漫反射光谱、X光电子能谱、循环伏安、热重-差热分析和X射线单晶衍射对其进行了表征.配合物晶体属单斜晶系,P2(1)/c空间群,晶胞参数:a=1.504 84(16)nm,b=2.966 8(3)nm,c=1.504 84(16)nm,β=117.82°,V=5.941 8(11)nm3,Dc=3.753 g/cm3,Z=4.结构分析表明,化合物分子由1个杂多阴离子,3个C7H10NO+阳离子和6个结晶水分子组成.电子光谱显示,在N,N-二甲基甲酰胺(DMF)溶剂中或固态情况下有机底物和杂多阴离子间存在电荷转移作用.热分析表明配合物的热分解分3步进行,其杂多阴离子分解温度为588.4℃.

A novel charge-transfer complex, （C7 H10 NO）3 [PW12O40]. 6H2O, was synthesized from tungstophosphoric acid and N-methyl-p-aminophenol sulfate, and characterized by elemental analysis, IR, UV-Vis, XPS, CV, TG-DTA and single crystal structural analysis. The crystal belongs to Monoclinic, Space group P2（1）/c,a=1. 504 84（16） nm,b=2. 966 8（3） nm,c=1. 504 84 （16） nm, β=117.82,V= 5. 941 8（11） nm^3, Dc= 3. 753 g/cm^3 ,Z=4. The title compound comprises of a heteropolyanion, three C7 H10NO＋ cations, and six crystallization water molecules. Electronic spectroscopy indicates the presence of charge transfer interaction between the organic substrate and the heteropolyanion in DMF solution and in the solid state. Thermal analysis shows that the complex has three stages of weight loss, and that its heteropolyanions decompose at 588.4℃. The cyclic voltammetric behavior of the title compound was also studied.