Acta Scientiarum Naturalium Universitatis Pekinensis

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Preparation and Spectroscopic Investigations of Lanthanide Complex of Polyoxometalate(Ⅰ)

ZONG Ruifa1, TIAN Wen1, WENG Shifu1, WU Jinguang1, YANG Yongli2, ZHAO Keping2, LIU Jingfu3   

  1. 1College of Chemistry and Molecular Engineering, State Key Laboratory of Rare Earth Materials Chemistry and Applications, Peking University, Beijing, 100871; 2Department of Chemistry, Capital Normal University, Beijing, 100037; 3Department of Chemistry, Northeast Normal University, Changchun, 130024
  • Received:1998-10-05 Online:1999-11-20 Published:1999-11-20

稀土多金属氧酸盐的合成及谱学研究 (Ⅰ)

宗瑞发1,田文1,翁诗甫1,吴瑾光1, 杨永丽2,赵克萍2,刘景福3   

  1. 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

Abstract: 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 ZnW12O406- , ZnW11O3910- is deformed, the W-Ob-W angle of ZnW11O3910- 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.

Key words: rare earth, 11-tungstozincate, polyoxometalate, complex, spectroscopy

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 α-Keggin 结构;电荷及电荷分布是影响 W-Od 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W-Ob-W键角减小,W-Oc-W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。

关键词: 稀土, 11-钨锌酸根, 多金属氧酸盐, 配合物, 谱学

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