利用二次球形配位构筑疏水型隧道框架结构  

Hydrophobic Channel Framework Constructed by Second-sphere Coordination

作　　者：袁雷[1] 郭放[1] 张爽[1] 胡志泉[1] 夏芳[1] 郭文生[1] 

机构地区：[1]辽宁大学化学学院,沈阳110036

出　　处：《高等学校化学学报》2007年第10期1897-1901,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20372031;20772054)资助.

摘　　要：质子化N,N,N′,N′-四苄基乙二胺(L)可与[MCl4]2-(M=Mn,Co,Cu)形成二次球形配合物.通过N—H…Cl相互作用构筑了1D带状和2D层状框架结构,层中配体L的苄基通过C—H…Cl相互作用分别采取水平和垂直取向,使1D带状和2D层状呈现凸凹交替排列.通过层间凸凹部位的C—H…H—C相互作用,形成了层间空穴,进而构筑成了3D疏水型隧道框架结构,乙醇分子能够填充于隧道之中.在L.2H+.[CuBr4]2-晶体中,由于[CuBr4]2-没有与配体L的苄基形成C—H…Br氢键,使配体L的苄基采取了同向取向.因而,形成的2D层状框架结构是平展的,未形成3D疏水型隧道框架结构,也未发现与乙醇分子的包结现象.Protonated N, N,N＇, N＇-tetrabenzyl-ethylenediamine （L） can form second-sphere complexes with [ MCl4]^2-（M = Mn, Co, Cu）. In these crystals, thick 1D ribbons and 2D layer frameworks are constructed through N-H…Cl interactions. The orientations of benzyl groups of compound L in the ribbon or layer are horizontal and perpendicular, respectively, through C-H…Cl interactions, so that the ribbon and layer with alternately convex-concave site arrangement are formed. The caves between layers are formed by C-H…H-C interaction of convex-concave sites on the layers, thus constructing a 3D hydrophobic channel framework, and alcohol molecules are accommodated in the channel. However, due to the absence of C-H…Br interactions between benzyls and [ CuBr4 ]^2- in L · 2H^＋· [ CuBr4 ]^2-, the orientation of benzyls of compound L adopts the same direction as a molecular long axis , thus, the 2D layer framework formed by compound L with [ CuBr4 ]^ 2- is planar, and the 3D hydrophobic channel framework and the inclusion of alcohol molecules are not observed.

关 键 词：N N N′ N′-四苄基乙二胺 晶体工程 二次球形配位 四氯合锰/钴/铜 四溴合铜 

分 类 号：O626[理学—有机化学]