Laboratoire de Chimie Supramoléculaire, Institut de Science et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg , 8 allée Gaspard Monge, 67000 Strasbourg, France.
State Key Laboratory of Supramolecular Structure and Materials, Jilin University , 2699 Qianjin Avenue, Changchun 130012, P. R. China.
J Am Chem Soc. 2017 Feb 15;139(6):2474-2483. doi: 10.1021/jacs.6b13072. Epub 2017 Feb 1.
The present study investigates the constitutional dynamic networks (CDNs) underlying dynamic covalent libraries (DCLs) that extend beyond the [2×2] case toward higher orders, namely [2×3] and [3×3] CDNs involving respectively six and nine constituents generated from the recombination of five and six components linked through reversible chemical reactions. It explores the behavior of such systems under the action of one or two effectors. More specifically and for the sake of proof of principle, it makes use of DCLs involving dynamic organic ligands and analyzes their single and double adaptive response under the action of one and two metal cation effectors. Thus, interconversions within [2×3] DCLs of six constituents (hydrazone, acylhydrazone, and imine ligands) give access to the generation of [2×3] CDNs of 3D trigonal prismatic type consisting of three [2×2] sub-networks and presenting specific responses to the application of Cu and Zn metal cation effectors, in particular double agonistic amplification. More complex [3×3] CDNs based on nine ligand constituents of imine, hydrazone, and acylhydrazone types were also designed and subjected to the application of one or two effectors, e.g., Cu and Fe metal cations, revealing novel types of adaptive behavior: (i) agonistic amplification between a single constituent and a full [2×2] sub-network, and (ii) agonistic amplification along a single diagonal connecting three constituents. Of special interest is also the dependence of the response of the system to hierarchical sequence of effector application, whereby initial interaction with Cu ions results in the destruction of the network, whereas the sequence Fe followed by Cu yields a clean three-constituent DCL. Finally and strikingly, the present results also demonstrate that the increase in complexity of the system by introduction of an additional entity leads to a simpler output through dynamic competition between components.
本研究调查了构成动态网络（CDN）的基础，这些网络扩展到超越[2×2]情况的更高阶，即涉及分别由通过可逆化学反应连接的五个和六个组分的重组产生的六个和九个组分的[2×3]和[3×3]CDN。它探讨了在一个或两个效应物作用下这些系统的行为。更具体地说，为了原理验证，它利用涉及动态有机配体的 DCL，并分析了它们在一个和两个金属阳离子效应物作用下的单一和双重自适应响应。因此，六个组分（腙、酰腙和亚胺配体）的[2×3]DCL 内的互变反应可生成由三个[2×2]子网络组成的 3D 三角棱柱型[2×3]CDN，并对 Cu 和 Zn 金属阳离子效应物的应用表现出特定的响应，特别是双重激动剂放大。还设计了基于亚胺、腙和酰腙类型的九个配体组分的更复杂的[3×3]CDN，并对一个或两个效应物（例如 Cu 和 Fe 金属阳离子）进行了应用，揭示了新型自适应行为：（i）单一成分与整个[2×2]子网络之间的激动剂放大，和（ii）连接三个成分的单个对角线的激动剂放大。特别有趣的是系统对效应物应用层次顺序的响应依赖性，其中与 Cu 离子的初始相互作用导致网络破坏，而 Fe 紧随 Cu 则产生干净的三组分 DCL。最后，令人瞩目的是，目前的结果还表明，通过引入额外实体增加系统的复杂性会导致通过组件之间的动态竞争产生更简单的输出。
