Dhers Sébastien, Holub Jan, Lehn Jean-Marie
Laboratoire de Chimie Supramoléculaire , ISIS , Université de Strasbourg , 8 Allée Gaspard Monge , 67000 Strasbourg , France . Email:
Chem Sci. 2017 Mar 1;8(3):2125-2130. doi: 10.1039/c6sc04662b. Epub 2016 Dec 8.
Dynamic Covalent Libraries (DCLs) have been used to demonstrate coevolution behaviour on a molecular level using dynamic covalent molecules such as imines and hydrazones. Two systems are presented: the first system is based on a dialdehyde and two diamines in combination with Zn(ii) and Hg(ii) to form a 2 × 2 Constitutional Dynamic Network (CDN) of four complexes of macrocyclic bis-imines. Whereas the two metal ions, when reacted separately form a complex with each macrocycle with low selectivity, when applied together, each cation yields selectively a complex with one of the two macrocycles. Thus, the simultaneous application of both cations, where one might have expected the formation of four different complexes, results in the synergistic evolution (co-evolution) towards a simpler, more selective outcome under agonist amplification. The second system of 4 components, 2 amines and 2 aldehydes displays metalloselection together with a correlated evolution in distribution on complexation of Zn(ii) and Cu(i) with the dynamic ligand constituents and exhibits a dynamic ratiometry process related to the antagonistic behaviour of a pair of ligand constituents.
动态共价库（DCLs）已被用于利用诸如亚胺和腙等动态共价分子在分子水平上展示协同进化行为。本文介绍了两个系统：第一个系统基于二醛和两种二胺，并与Zn(ii)和Hg(ii)结合，形成由四个大环双亚胺配合物组成的2×2结构动态网络（CDN）。当两种金属离子分别反应时，它们与每个大环形成配合物的选择性较低，但当一起应用时，每个阳离子会选择性地与两个大环之一形成配合物。因此，同时应用两种阳离子时，原本可能预期会形成四种不同的配合物，但结果是在激动剂放大作用下朝着更简单、更具选择性的结果协同进化（共同进化）。第二个由4种成分（2种胺和2种醛）组成的系统在Zn(ii)和Cu(i)与动态配体成分络合时表现出金属选择性以及相关的分布协同进化，并展示了与一对配体成分的拮抗行为相关的动态比率测定过程。
