二次配体结构和[CuCl_4]^(2-)构型对层间隧道结构的影响研究  

Study on the Effects of Structure of Second Ligands and [CuCl_4]^(2-) Configuration on Channel Framework between Layers

作　　者：郭放[1] 夏芳[1] 宋纯亮[1] 郭文生[1] 

机构地区：[1]辽宁大学化学院,沈阳110036

出　　处：《化学学报》2009年第16期1891-1896,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(No20772054)资助项目

摘　　要：设计合成的质子配体,N,N,N',N'-四(对甲基苄基)乙二胺(SL1)和N,N,N',N'-四苄基乙二胺(SL2),是连有大体积取代基团的含N双齿配体,它可通过二次球形配位,与第一络合物[CuCl4]2-形成层间隧道框架结构.环戊醇分子和乙醇分子分别被填入由SL1和SL2构筑的隧道中,形成包结化合物.晶体结构分析结果表明,这样的配体易于与指导基团通过NH+…Cl-氢键作用进行双齿配位并形成1D带和2D层结构;SL12D层间的苄基呈平行堆砌,形成1D亲水性隧道框架,SL22D层间的苄基呈交错堆砌,形成了1D疏水性隧道框架.实验结果表明,层间隧道框架结构的孔径及极性与第二配体的分子长度、指导基团的构型以及客体分子的形状大小有关.The designed and synthesized protonated ligands, N,N,N′,N′tetra-（p-methylbenzyl）ethylenediamine （SL1） and N,N,N′,N′-tetra-benzylethylenediamine （SL2）, are both the N-bidentate ligands with the bulky substituent groups, and can form the channel between layers with the directional group [CuCl4]^2- through the second-sphere coordination. Molecules of cyclopentyl alcohol and ethyl alcohol are accommodated in the channel constructed by SL1 and SL2, respectively, thus forming the inclusion compounds. The analysis results of crystal structure show that such ligands are easy to form bidentate complexes with [CuCl4]^2- by NH^＋…Cl^- hydrogen bond and construct 1D ribbon and 2D layer structure. In the crystal of SL1, benzyl groups of SL1 between 2D layers stack in parallel motif, leading to 1D hydrophilic channel framework between layers; while in the crystal of SL2, the benzyl groups of SL2 between 2D layers stack in staggered motif, resulting in 1D hydrophobic channel framework between layers. The experimental results show that the size and polarity of channel framework are affected by the molecule length of second ligand, configuration of [CuCl4]^2-, and the shape, size of the guest molecules.

关 键 词：N N N′ N′ -四(对甲基苄基)乙二胺 N N N′ N′-四苄基乙二胺 二次球形配位 层间隧道 包结化合物 

分 类 号：O641.4[理学—物理化学]