利用二次球形配位构筑疏水型隧道框架结构

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.

Hydrophobic Channel Framework Constructed by Second-sphere Coordination

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.