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

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.