含手性二硫代双缩脲单元的配位聚合物的一锅法合成及晶体结构  

One-pot synthesis and crystal structure of chiral dithiobiuret type coordination polymer

作　　者：孙金时 陈鹏[1,2] 赵念[1,2] 贺鸿明 刘国杰[2] 朱广山[1,2] 

机构地区：[1]吉林大学无机合成与制备化学国家重点实验室,长春130012 [2]吉林大学化学学院,长春130012

出　　处：《中国科技论文》2015年第12期1369-1372,共4页China Sciencepaper

基　　金：高等学校博士学科点专项科研基金资助项目(20130061120016);国家自然科学基金资助项目(21302061);中国博士后科学基金资助项目(2013T60318;2012M510130)

摘　　要：为了将手性二硫代双缩脲单元引入到配位聚合物晶体中,采用(1R,2R)-(-)-1,2-环己二胺的双异硫氰酸酯衍生物和3-氨基吡啶原位生成二硫代双缩脲官能团,然后利用扩散法在一锅内和Cd(NO3)2·4H2O合成了一种含手性二硫代双缩脲单元的配位聚合物晶体。并用X射线单晶衍射仪测定了其结构,确定了二硫代双缩脲官能团在晶体中的配位方式。结果表明:该配合物结晶于正交晶系,每个不对称结构单元中含有1个镉离子和2个配体分子,中心镉离子采取八面体六配位方式,与4个硫原子和2个吡啶环中的氮原子配位;每个配体中二硫代双缩脲单元的2个硫原子与1个镉离子螯合,而同一配体中的吡啶氮原子与另一个镉离子配位,从而形成一条一维链状结构;通过氢键作用将一维链状结构相互连接,从而形成三维结构。A facile one-pot synthesis of a novel chiral dithiobiuret type crystalline coordination polymer was achieved using diffu-sion method,by layering a solution of （1R,2R）-（-）-1,2-diisothiocyanatocyclohexane and 3-aminopyridine in CH3 OH upon a so-lution of Cd（NO3 ）2 ·4H2 O in H2 O.The crystal structure was characterized by single-crystal X-ray diffraction,and the unprece-dented coordination mode between dithiobiuret unit and metal center was elucidated.The results show that this complex crystalli-zes in orthorhombic system.The asymmetric unit contains one cadmium ion and two ligands.The cadmium ion adopts an octahe-dral coordination geometry and is six-coordinated by four sulfur atoms and two nitrogen atoms.The two sulfur atoms of dithiobi-uret unit from one ligand coordinate with one cadmium ion,while the pyridine nitrogen atom from the same ligand coordinates with another cadmium ion,forming a one-dimensional chain.These one-dimensional chains are further linked each other into a three-dimensional supramolecular structure through hydrogen bonds.

关 键 词：金属有机聚合物 结晶聚合物 手性二硫代双缩脲 一锅法合成 扩散法 

分 类 号：O641.4[理学—物理化学]