A Perspective on Carbon–Carbon Diradical-Mediated Dynamic Covalent Synthesis of Organic Macrocycles and Their Emerging Functions

A biological self-assembly of organized supramolecular structures and functional materials has emerged as a significant research focus in recent decades. Different self-assembly strategies have been proposed and successfully adopted for engineering complex supramolecular structures. Among others, substantial research progress has been made in using dynamic covalent chemistry (DCC) to generate supramolecular structures with sophisticated functional properties. This Perspective elaborates on the role of carbon–carbon (C–C)-based diradical-based DCC in supramolecular self-assembly. It provides an in-depth discussion of the structural aspects of C–C dynamic covalent bonds in discrete oligomer formation including dimers, trimers, tetramers, and hexameric structures. Early sections survey critical factors contributing to the longevity and stability of radical systems and influences of substitution on the self-assembly of diradicals into dimers or macrocycles. Significant attention has been given to the dynamic characteristics of diradical bonds and the impact of hydrogen bonds and π–π interactions on the structural configurations of self-assembled structures. The latter part of this article elaborates on the functional properties and applications of DCC-mediated self-assembled structures. The primary objectives of this review are to (i) present a detailed analysis of the benefits associated with C–C dynamic covalent chemistry in the formation of diradical-mediated self-assembled structures and (ii) investigate their functional properties.