铜-有机多酸配合物[CuI(2,2'-bipy)_2]{[CuII(2,2'-bipy)_2]_2(BW_(12)O_(40))}·4H_2O的原位合成、晶体结构与表征

In-situ Synthesis,Crystal Structure and Characterization of Copper-organic Polyacid Complex [CuI(2,2'-bipy)_2]{[CuII(2,2'-bipy)_2]_2-(BW_(12)O_(40))}·4H_2O

在水热条件下,K5BW12O4·nH2O,CuSO4·5H2O,2,2'-联吡啶-3,3'-二羧酸在水溶液中进行原位反应,得到一维链状化合物[CuI(2,2'-bipy)2]{[CuII(2,2'-bipy)2]2(BW12O40)}·4H2O,并对其进行了元素分析,IR,TG,CV和单晶X射线衍射表征.结果表明,化合物属于单斜晶系,P21/n空间群,晶胞参数a=1.88365(14)nm,b=2.04178(15)nm,c=2.16724(16)nm,α=90°,β=96.6720(10)°,γ=90°,V=8.2786(11)nm3,Z=4,Dc=3.255g/cm3,R1=0.0575,wR2=0.1073.化合物分子结构单元由1个铜-有机多酸阴离子{[CuII(2,2'-bipy)2]2(BW12O40)}-,1个配位阳离子[CuI(2,2'-bipy)2]+,4个结晶水分子构成.化合物分子通过氢键和π-π堆积作用形成二维超分子体系.电化学研究表明,化合物存在三步氧化还原过程.

A novel copper-organic polyacid complex [CuI（2,2＇-bipy）2]{[CuII（2,2＇-bipy）2]2（BW12O40）}·4H2O was synthesized by in-situ generation of 2,2＇-bipyridine from 2,2＇-bipyridine-3,3＇-dicarboxylate precursor under hydrothermal condition and characterized by elemental analysis,IR,TG,CV and single-crystal X-ray diffraction.The title compound crystallized in a monoclinic crystal system,with space group P21/n,a= 1.88365（14） nm,b=2.04178（15） nm,c=2.16724（16） nm,α=90°,β=96.6720（10）°,γ=90°,V= 8.2786（11） nm3,Z=4,Dc=3.255 g/cm3,R1=0.0575,wR2=0.1073.The compound consists of copper-organic polyoxoanion {[CuII（2,2＇-bipy）2]2（BW12O40）}-,cations [CuI（2,2＇-bipy）2]＋,lattice water molecules and formed a 2D supramolecular networks by hydrogen bond and π-π stacking of 2,2＇-bipyridine.The cyclic voltammogram indicated that three couples redox waves were observed on the compound modified carbon paste electrode （1-CPE）.