Courtois Jérémie, Wang Bin, Abdul-Hassan Wathiq S, Almásy László, Yan Minhao, Royal Guy
State Key Laboratory of Environment-friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, China.
Centre for Energy Research, Konkoly Thege Miklós Street, No. 29-33, Budapest-1121, Hungary.
Inorg Chem. 2020 May 4;59(9):6100-6109. doi: 10.1021/acs.inorgchem.0c00161. Epub 2020 Apr 14.
Colloidal particles based on supramolecular polymers are emerging as promising functional materials because of their intrinsic dynamic features and the possibility of stimuli responsivity. In this work, ≈200 nm self-assembled redox-responsive colloidal particles made of 1D-coordination polymers were readily prepared. In these metallopolymers, organic entities made of bis(viologen) groups covalently associated with terpyridine units are spontaneously bridged by Zn cations through the formation of coordination bonds. The properties of these particles were analyzed and their redox activities investigated. Upon reduction of the viologen units, the formation of π-dimers between the reduced viologen moieties was demonstrated by spectroscopic experiments. It was shown that intermolecular π-dimers (i.e., between different polymer chains) that do not exist in homogeneous polymer solutions were, nevertheless, formed in the particle's structure because of the effects of confinement. The presence of these π-dimers allows stabilization of the charge in the colloids.
基于超分子聚合物的胶体颗粒因其固有的动态特性和刺激响应性的可能性，正成为有前途的功能材料。在这项工作中，由一维配位聚合物制成的约200纳米自组装氧化还原响应胶体颗粒很容易制备。在这些金属聚合物中，由双（紫精）基团与三联吡啶单元共价结合而成的有机实体通过形成配位键被锌阳离子自发桥连。分析了这些颗粒的性质并研究了它们的氧化还原活性。通过光谱实验证明，在紫精单元还原后，还原的紫精部分之间形成了π-二聚体。结果表明，由于受限效应，在均相聚合物溶液中不存在的分子间π-二聚体（即不同聚合物链之间）在颗粒结构中形成。这些π-二聚体的存在使胶体中的电荷得以稳定。
