Recent Progress in Constructing Structurally Ordered Polymeric Architectures via Dynamic Covalent Chemistry

Although dynamic covalent chemistry (DCvC) has been widely utilized to synthesize small molecules and polymers, it remains challenging to construct highly ordered polymeric architectures via DCvC. Further exploration of novel dynamic linkages (in addition to commonly used imine and boronate ester) will expand the library of readily accessible dynamic linkages, diversify the polymeric structures, and unlock new functionality. In this mini-review, the DCvC-based synthetic strategies for enhancing the structural orders of polymeric architectures will be discussed from both thermodynamic control and kinetic control aspects. The relationship between the structure, stability, and dynamic behavior of a DCvC bond will be presented. Then recent examples of constructing polymers with DCvC and supramolecular bonding interactions, such as metal-ligand coordination, host-guest binding, and hydrogen bonding, will be reviewed to demonstrate their synergistic relationship. Furthermore, polymers featuring relatively unexplored DCvC will be highlighted to underscore how developing novel dynamic linkages and fundamental DCvC studies can broaden the scope of functional polymeric architectures. In the end, the challenges in the current field and possible future directions will also be discussed. Advancements using these design principles will undoubtedly lead to the development of intriguing chemistries, polymeric architectures, and functionality.