β-环糊精与2,2'-联吡啶和4,4'-联吡啶形成的配合物的结合能力及组装行为

Binding ability and assembly behavior of beta-cyclodextrin complexes with 2,2'-dipyridine and 4,4'-dipyridine.

作者信息

Liu Yu, Zhao Yan-Li, Zhang Heng-Yi, Yang En-Cui, Guan Xu-Dong

机构信息

Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, PR China.

出版信息

J Org Chem. 2004 May 14;69(10):3383-90. doi: 10.1021/jo035868x.

DOI:10.1021/jo035868x

PMID:15132546

Abstract

Two channel-type supramolecular aggregations 1 and 2 were prepared by the inclusion complex of beta-cyclodextrin with 2,2'-dipyridine and 4,4'-dipyridine, respectively, and their binding ability and assembly behavior were investigated comprehensively by X-ray crystallography, (1)H NMR, circular dichroism spectra, and microcalorimetric titration in solution and the solid state. The obtained results revealed that the hydrogen bonds and pi-pi stacking interactions are crucial factors for the formation of the molecular aggregations containing beta-cyclodextrin and dipyridines. The disparity of nitrogen atom position in dipyridines leads not only to the distinct crystal system and space group, i.e., monoclinic system (C2) for 1 and triclinic system (P-1) for 2, but also different binding modes and thermodynamical parameters upon complexation of 2,2'-dipyridine and 4,4'-dipyridine with beta-cyclodextrin in aqueous solution.

摘要

分别通过β-环糊精与2,2'-联吡啶和4,4'-联吡啶的包合物制备了两种通道型超分子聚集体1和2，并通过X射线晶体学、¹H NMR、圆二色光谱以及溶液和固态中的微量热滴定对它们的结合能力和组装行为进行了全面研究。所得结果表明，氢键和π-π堆积相互作用是形成含β-环糊精和联吡啶的分子聚集体的关键因素。联吡啶中氮原子位置的差异不仅导致了不同的晶体系统和空间群，即1为单斜晶系（C2），2为三斜晶系（P-1），而且还导致2,2'-联吡啶和4,4'-联吡啶与β-环糊精在水溶液中络合时具有不同的结合模式和热力学参数。