基于自组装生成[Bi_2W_(21)O_(70)(OH)_3]^(11-)配体的双核Ce(Ⅳ)配合物合成、结构及电化学性质  

Synthesis,structure and electrochemical property of a binuclear Ce(Ⅳ) complex based on self-assembly [Bi_2W_(21)O_(70)(OH)_3]^(11-) as ligand

作　　者：辛颖[1] 王蕾 贺帅 由万胜[1] 

机构地区：[1]辽宁师范大学化学化工学院,辽宁大连116029

出　　处：《分子科学学报》2017年第5期430-435,共6页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(21573099)

摘　　要：使用[β-B-BiW_9O_(33)]^(9-)作为基本建筑单元,成功合成了多酸做配体的双核Ce(Ⅳ)配合物(Na_6H_(10){Ce(H_2O)_3(μ_2-OH)[Bi_2W_(21)O_(70)(OH)_3]}_2·40H_2O),通过元素分析、X-射线单晶衍射、XRD、IR和TG表征技术确定了其组成和结构.两核Ce(Ⅳ)离子配合物是通过2个μ_2-OH^-连接构成的,每个Ce(Ⅳ)离子除了与2个μ_2-OH^-配位外,还与3个H_2O以及[Bi_2W_(21)O_(70)(OH)_3]^(11-)中4个缺位O原子配位,形成三帽三棱柱.[Bi_2W_(21)O_(70)(OH)_3]^(11-)多酸阴离子是通过3个W(Ⅵ)连接形成新的多酸阴离子物种,在缺位结构上留有一个空位恰好与Ce(Ⅳ)离子配位.通过对配合物的电化学分析发现,与硝酸铈铵对比,配合物中Ce(Ⅳ/Ⅲ)的阳极峰电势由0.857减小至0.772V,表明多酸阴离子配体有稳定Ce(Ⅳ)的作用.A binuclear Ce（Ⅳ）complex,Na6H（10）{Ce（H2O）3（μ2-OH）[Bi2W（21）O（70）（OH）3）}2·40 H2O,was successfully synthesized by using[β-B-BiW9O（33）]（9-）as a basic building unit and was determined by elemental analysis,single crystal X-ray diffraction,XRD,IR,TG.The two Ce（Ⅳ）ions in the compex is linked by two brigdingμ2-OH-ions.In addition to two μ2-OH-ions,each Ce（Ⅳ）ion is coordinated with three H2O molecules and four oxygen atoms of[Bi2W（21）O（70）（OH）3]（11-）,forming a threecapped triangular prism configuration.The [Bi2W（21）O（70）（OH）3]（11-）anion is constructed with two [β-BBiW9O（33）]（9-）anions by three WO6 octahedra,leaving a vacancy to coordinate with Ce（Ⅳ）ions.The electrochemical analysis showed that the peak potential of Ce（Ⅳ/Ⅲ）in complex was reduced from 0.857 to 0.772 V,which indicated that the polyoxometalate anion ligand plays a role in stabilizing Ce（Ⅳ）ions.

关 键 词：多金属氧酸盐 缺位钨铋酸盐 Ce(Ⅳ)离子 

分 类 号：O614[理学—无机化学]