摘要
在水热环境下,将Na10[α-SiW9O34]爛18H2O和CuCl2爛2H2O在2,2′-联咪唑和4,4′-联吡啶存在下反应合成一种饱和Keggin硅钨酸盐杂化物[Cu(biim)2]4[α-SiW12O40]2爛4H2O(1),并通过红外光谱,X射线光电子能谱和X射线单晶衍射进行了结构表征.化合物1分子包含2个中性的Keggin[Cu(biim)2]2[α-SiW12O40]单元和4个结晶水分子.值得注意的是在[α-SiW12O40]4-单元中,与硅原子相连的每个氧原子无序排列在两个位置,这导致了硅原子呈现立方体的几何构型.中性Keggin型[Cu(biim)2]2[α-SiW12O40]单元具有中心对称性,两个[Cu(biim)2]2+配离子对称连接在[α-SiW12O40]4-的两端.邻近的[Cu(biim)2]2[α-SiW12O40]单元之间通过氢键作用形成三维的超分子结构.
The hydrothermal reaction of Na10[α-SiW9O34]·18H2O with CuCl2 · 2H2 O in the presence of 2,2P-biimdazole （biim） and 4,4＇-bipyridine （4,4＇-bpy） resulted in a saturated Keg- gin silicotungstate （ST） hybrid [Cu（biim）_2]_4[α-SiW_（12）O_（40）]_2·4H_2O
（1）, which was structur- ally characterized by IR spectroscopy, X-ray photoelectron spectroscopy （XPS） and X-ray sin- gle-crystal diffraction. The molecular structure of 1 is made up of two neutral Keggin-type [Cu（biim）2]2[α-SiW12O40] units and four crystal water molecules. It should be noted that each ox- ygen atom bonding to the Si atom in [α-SiW12O40]4- polyoxoanion （POA） is disordered over two positions, which leads to the cubic coordination geometry of the Si atom. The neutral Keg- gin-type [Cu（biim）2]2[α-SiW12O40] unit is centrosymmetric and two [Cu（biim）2]2＋ cations link to both sides of the [α-SiW12O40]4- POA. Adjacent [Cu（biim）2]2[α-SiW12O40] units are connected together through hydrogen bond interactions giving rise to a 3D supramolecular structure.
出处
《化学研究》
CAS
2015年第3期251-257,共7页
Chemical Research
基金
Supported by the Natural Science Foundation of China(21301049,U1304208)
the Natural Science Foundation of Henan Province(122300410106)
the Students Innovative Pilot Plan of Henan University(2013,2014)
