硅钨酸盐[H_2bpy][H_2bbpy][α-SiW_(12)O_(40)]·2H_2O的合成与结构表征  

Synthesis and structural characterization of a silicotungstate [H_2bpy][H_2bbpy][α-SiW_(12)O_(40)]·2H_2O

作　　者：陈利娟[1,2] 元静[1] 罗婕[1,2] 赵俊伟[1] 

机构地区：[1]河南大学化学化工学院河南省多酸化学重点实验室,河南开封475004 [2]河南大学基础实验教学中心,河南开封475004

出　　处：《化学研究》2013年第4期365-369,共5页Chemical Research

基　　金：国家自然科学基金(21101055);河南省科技厅自然科学基金(122300410106);河南省教育厅自然科学基金(2009A150003;2010B150006);2012年河南大学大学生创新性实验计划项目

摘　　要：以Na10[A-α-SiW9O34].18H2O、CuCl2.2H2O、EuCl3、联咪唑、4,4′-联吡啶为原料,利用水热法合成了有机-无机复合Keggin结构硅钨酸盐[H2bpy][H2bbpy][α-SiW12O40].2H2O[bpy=4,4′-bipyridine,bbpy=N-(2-(4,4′-bipyridyl))-4,4′-bipyridine],并借助元素分析、红外光谱和X射线单晶衍射对其组成和结构进行了表征.结果表明,标题化合物属于单斜晶系,P2(1)/c空间群,晶胞参数为:a=1.149 92(13)nm,b=2.137 6(3)nm,c=2.248 2(3)nm,β=98.406(2)°,V=5.466 7(111)nm3,Z=4,Dc=4.109g/cm3,GOOF=1.038,R1=0.057 5,wR2=0.118 4.其分子由1个饱和的硅钨酸盐[α-SiW12O40]4-阴离子,1个游离的双质子化[H2bbpy]2+阳离子,1个游离的双质子化[H2bpy]2+阳离子和2个结晶水分子组成.值得指出的是,4,4′-联吡啶分子在水热条件下发生反应,形成N-(2-(4,4′-联吡啶基))-4,4′-联吡啶.An organic inorganic composite Keggin-type silicotungstate denoted as[H2bpy][H2bbpy][α-SiW12O40].2H2O（bpy = 4,4′-bipyridine,bbpy = N-（2-（4,4′-bipyridyl））-4,4′-bipyridine）was synthesized via a hydrothermal route with Na10[A-α-SiW9O34].18H2O,CuCl2.2H2O,EuCl3,diimidazole and 4,4′-bipyridine as the starting materials.The composition and structure of as-synthesized product were analyzed by elemental analysis,infrared spectrometry and single-crystal X-ray diffraction.Results indicate that the title compound crystallizes in the monoclinic system of space group P2（1）/c,with crystal cell parameters of a = 1.149 92（13） nm,b=2.137 6（3）nm,c=2.248 2（3）nm,β=98.406（2）°,V =5.466 7（111）nm3,Z = 4,Dc=4.109g/cm3,GOOF = 1.038,R1= 0.057 5,and wR2= 0.118 4.Besides,it consists of 1saturated silicotungstate[α-SiW12O40]4-anion,1free diprotonated[H2bbpy]2＋cation,1free diprotonated[H2bpy]2＋cation and 2lattice water molecules.It is worth mentioning that N-（2-（4,4′-bipyridyl））-4,4′-bipyridine is formed by the fusion of two 4,4′-bipyridines under hydrothermal conditions.

关 键 词：多金属氧酸盐 硅钨酸盐 合成 结构表征 

分 类 号：O614.61[理学—无机化学]