State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China.
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China.
J Am Chem Soc. 2022 Aug 24;144(33):14962-14975. doi: 10.1021/jacs.2c02434. Epub 2022 Aug 15.
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.
二聚体可能是最简单的模型，可以帮助理解在聚合体、晶体和其他固态等大大扩展的系统中发生的基本物理和化学过程。二聚体中的分子相互作用使其有别于相应的单体状态，并决定其特性。通过施加超分子限制对非共价二聚体进行分子工程，可以对分子相互作用进行额外的控制，特别是对其动态方面。本观点介绍了在非共价二聚体的分子工程方面所做的最新努力，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基于分子的材料更好的性能和/或功能，例如增强的发射、室温磷光和有效的催化。我们特别讨论了伪静态二聚体，它们可以长时间维持分子相互作用，但仍然足够灵活以适应变化。伪静态特性允许活性物质沿着替代途径衰减，从而产生从传统动态系统不容易获得的新兴特征。
