清华大学张希团队报道了非共价二聚反应的分子工程。相关研究成果于2022年8月15日发表于国际一流学术期刊《美国化学会杂志》。

二聚体可能是有助于理解在聚集体、晶体和其他固态等扩展系统中发生的基本物理和化学过程的最简单模型。二聚体内的分子相互作用将其与相应的单体状态区分开来，并确定其特征。通过应用超分子限制进行非共价二聚的分子工程可以对分子间的相互作用进行额外的控制，特别是在其动态方面。

该文介绍了最近在非共价二聚分子工程方面所做的研究，包括超分子二聚体、折叠二聚体和大环二聚体。它展示了超分子限制的变化如何赋予分子基材料更好的性能和/或功能，如增强的发射、室温磷光和有效的催化作用。研究人员特别讨论了伪静态二聚体，它可以长时间维持分子间的相互作用，但仍然足够灵活以适应变化。伪静态特征使活性物种沿替代路径衰减，从而衍生出传统动态系统不易获得的新特征。

附：英文原文

Title: Molecular Engineering of Noncovalent Dimerization

Author: Guanglu Wu, Fei Li, Bohan Tang, Xi Zhang

Issue&Volume: August 15, 2022

Abstract: Dimers are probably the simplest model to facilitate the understanding of fundamental physical and chemical processes that take place in much-expanded systems like aggregates, crystals, and other solid states. The molecular interplay within a dimer differentiates it from the corresponding monomeric state and determines its features. Molecular engineering of noncovalent dimerization through applied supramolecular restrictions enables additional control over molecular interplay, particularly over its dynamic aspect. This Perspective introduces the recent effort that has been made in the molecular engineering of noncovalent dimerization, including supramolecular dimers, folda-dimers, and macrocyclic dimers. It showcases how the variation in supramolecular restrictions endows molecular-based materials with improved performance and/or functions like enhanced emission, room-temperature phosphorescence, and effective catalysis. We particularly discuss pseudostatic dimers that can sustain molecular interplay for a long period of time, yet are still flexible enough to adapt to variations. The pseudostatic feature allows for active species to decay along an alternate pathway, thereby spinning off emerging features that are not readily accessible from conventional dynamic systems.

DOI: 10.1021/jacs.2c02434

Source: https://pubs.acs.org/doi/10.1021/jacs.2c02434