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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
【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.
【Abstract】 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.
【Key words】 N,N,N′,N′-Tetrabenzyl-ethylenediamine; Crystal engineering; Second-sphere coordination; [MnCl4/CoCl4/CuCl4]2-; [CuBr4]2-;
- 【文献出处】 高等学校化学学报 ,Chemical Journal of Chinese Universities , 编辑部邮箱 ,2007年10期
- 【分类号】O641.4
- 【被引频次】4
- 【下载频次】74