稀土多金属氧酸盐的合成及谱学研究(Ⅰ) Na_(17)[Ln(ZnW_(11)O_(39))_2]·xH_2O体系  

Preparation and Spectroscopic Investigations of Lanthanide Complex of Polyoxometalate(Ⅰ) Na_(17)[Ln(ZnW_(11)O_(39))_2]·xH_2O

作　　者：宗瑞发[1] 田文 翁诗甫[1] 吴瑾光[1] 杨永丽[2] 赵克萍 刘景福 

机构地区：[1]北京大学化学与分子工程学院,稀土材料化学与应用国家重点实验室,北京100871 [2]首都师范大学化学系,北京100037 [3]东北师范大学化学系,长春130024

出　　处：《北京大学学报（自然科学版）》1999年第6期727-733,共7页Acta Scientiarum Naturalium Universitatis Pekinensis

基　　金：国家重点基础研究发展规划资助;国家自然科学基金!( 2 96710 0 2 );北京市科委资助项目

摘　　要：报道了双(11钨锌酸根)合稀土(Ⅲ)酸钠(稀土=La,Pr,Nd,Tb,Er)的合成及红外、拉曼和漫反射紫外可见等谱学方法的研究工作。振动光谱研究表明,11钨锌酸根配体为不饱和αKeggin结构;电荷及电荷分布是影响WOd振动的主要因素;配合物中负电荷被比较均匀地分布于整个负离子。与ZnW12O406-相比,稀土配合物中WObW键角减小,WOcW键角增大,ZnW11O3910-配体发生变形。电子光谱研究表明标题配合物中不存在对称中心,其中稀土离子的配位数为8,这与稀土离子的四方反棱柱型配位几何是一致的。A series of novel rare earth coordination compounds,sodium salt of bis(undecatungstozincate) lanthanide(Ⅲ),was synthesized and characterized by the means of FTIR,FT\|Raman as well as Diffuse Reflectance techniques.Vibrational studies show that the ligand is defect α Keggin type.The electronic charge and its distribution on the anion are the main factors affecting the W\|Od vibration.The negative charge is almost evenly distributed among the whole polyoxometalate complex.Compared with ZnW 12 O 40 6- ,ZnW 11 O 39 10- is deformed,the W\|Ob\|W angle of ZnW 11 O 39 10- is smaller and the W\|Oc\|W angle is greater.Electronic spectroscopic investigations demonstrate that there is no inversion center in the complex and the coordination number of the lanthanide element in the complex is about eight,which is possibly consistent with antiprism structure of the rare earth.

关 键 词：钨锌酸根 多金属氧酸盐 配合物 谱学 稀土 

分 类 号：O614.33[理学—无机化学]