多孔金属有机骨架[Cd_3(PA-BIM)_6(BF_4)_6]·34H_2O的结构与可逆吸附的三维水簇网络  

Crystal structure of porous metal-organic framework[Cd_3(PA-BIM)_6(BF_4)_6]·34H_2O and reversible absorption of 3D water cluster

作　　者：周俊强 张鲲鹏 施少敏 金传明 

机构地区：[1]稀有金属化学湖北省协同创新中心污染物分析与资源化技术湖北省重点实验室湖北师范大学化学化工学院,湖北黄石435002

出　　处：《化学研究与应用》2017年第10期1537-1543,共7页Chemical Research and Application

基　　金：国家自然科学基金项目(21171053)资助;湖北省高校优秀中青年科技创新团队(T201311)资助

摘　　要：利用配体1,1-二[2-(苯基偶氮基)-1-咪唑基]甲烷(PA-BIM)与Cd(BF4)2作用,溶液扩散法得到了一个包结三维水簇网络的三维金属有机骨架化合物[Cd_3(PA-BIM)_6(BF_4)_6]·34H_2O(1)。晶体结构表明:金属镉以四面体方式同四个配体PA-BIM的反式构象配位,形成了一个三维的多孔金属有机阳离子骨架结构,多孔的结构中包结一个具有高度对称的三维水簇网格分子,具有由"书本型"构象六员水环与五员水环相互稠环而成的呈笼状结构(H_2O)_(14)簇单元,呈现液态水的结构特征。红外光谱、X-射线粉末衍射及热重分析结果均表明三维水簇分子具有可逆吸附性质,且三维水簇分子与金属有机阳离子骨架没有经典的氢键作用。A novel 3D metal-organic framework[Cd3（PA-BIM）6（BF4）6]·34H2O（1）（where PA-BIM is 1,1-bis[（2-phenylazo）imidazol-1-yl]methane） encapsulated within an unusual 3D water cluster has been synthesized by the reaction of Cd（BF4）2 and ligand PA-BIM at room temperature using slowly diffuse methodology.The crystal structure reveals that 1 has a porous 3D metal-organic cationic framework with tetrahedron coordinated Cd（II） centers and trans-conformation PA-BIM ligands.These holes are occupied by an fascinating three-dimensional water clathrate network which consists of cage-shaped structural tetradecameric water cluster（H2O）14 units with fused ＂book＂ conformation water hexamer and cyclic water pentamer.The supramolecular（H2O）14 morphology is similar to liquid water.The reversible absorption of 3D water cluster was characterized by IR,XRD and TGA.There are not typical hydrogen bonding interactions between the 3D water clathrate network and the cationic skeleton of metal-organic framework.

关 键 词：三维金属有机骨架 晶体结构 三维水簇 可逆吸附 (H2O)14簇 

分 类 号：O641.3[理学—物理化学]