Dawson结构聚金属氧酸盐有机-无机复合物[{Y(DMSO)_(5)(H_(2)O)_(3)}{Y(DMSO)_(8)}][P_(2)W_(18)O_(62)]·2DMSO·2H_(2)O的合成、性质及晶体结构  

Synthesis, Characterization and Crystal Structure of a Polyoxometalate-Based Organic-Inorganic Compound, [{Y(DMSO)_(5)(H_(2)O)_(3)}{Y(DMSO)_(8)}] [P_(2)W_(18)O_(62)]·2DMSO·2H_(2)O

作　　者：王敬平[1] 郭东杰[1] 牛景扬[1] WANG Jing—Ping;GUO Dong-Jie;NIU Jing-Yang(School of Chemistry and Engineering,He’nan University,Kaifeng 475001)

机构地区：[1]河南大学化学化工学院,开封475001

出　　处：《无机化学学报》2003年第6期579-584,共6页Chinese Journal of Inorganic Chemistry

基　　金：河南省杰出青年基金;河南省教育厅基金资助项目(No.20011500024)。

摘　　要：以α-H_(6)P_(2)W_(18)O_(62)·nH_(2)O,Y_(2)O_(3),DMSO(二甲亚砜)为原料合成了Dawson结构聚金属氧酸盐有机-无机复合物[Y(DMSO)5(H_(2)O)_(3)][Y(DMSO)_(8)][P_(2)W_(18)O_(62)]·2DMSO·2H_(2)O(1),化合物晶体属于单斜晶系,P2_(1)/c空间群,Mr=5803.06,a=1.7614(4)nm,b=3.1527(6)nm,c=2.1523(4)nm,β=90.40(3)°,V=11.963(4)nm^(3),Dc=3.222g·cm^(-3),μ=18.566mm^(-1),Z=4,F(000)=10464。由17342个可观测衍射点犤I≥2σ(I)犦用于精修所有的结构参数,得一致性因子R=0.0745,wR=0.1438。结构解析表明,化合物中两个Y^(3+)离子的配位环境均为八配位的畸变双冠三棱柱构型。CV行为研究表明,标题化合物中阴离子(pH=5.5)存在五步还原过程,得电子数依次为1,1,1,1,2。化合物的IR光谱和X-射线衍射结果表明,固态条件下配阳离子与杂多阴离子之间存在较强的相互作用。A composite compound of[{Y(DMSO)_(5)(H_(2)O)_(3)}{Y(DMSO)_(8)}]·2DMSO·2H_(2)O was synthesized from Y_(2)O_(3),DMSO andαH_(6)P_(2)W_(18)O_(62)·nH_(2)O in mixed solvent of acetonitrile and water.Its structure was characterized via elemental analysis,IR,and single crystal X ray diffraction analysis.The title compound crystallizes in a monocline lattice,P2_(1)/c,with a=1.7614(4)nm,b=3.1527(6)nm,c=2.1523(4)nm,β=90.40(3)°,V=11.963(4)nm^(3),Mr=5803.06,Z=4,Dc=3.222g·cm^(-3),μ=18.566mm-1,F(000)=10464,R=0.0745 and wR=0.1438.The result of crystal structure analysis indicates that both Y3+ions are eight coordinated and the coordination polyhedra around two Y3+ions attribute to bicapped distorted trigonal prism.Cyclic Voltammetry of compound(1mmol·L^(-1),pH=5.5)in the presence of Na_(2)SO_(4)(0.1mol·L^(-1))reveals five steps(one,one,one,one,two electron)reductions.CCDC:199158.

关 键 词：DAWSON结构 磷钨酸 合成 晶体结构 有机-无机复合物 

分 类 号：O611.66[理学—无机化学]