Kinetic Control of Self‐Assembly Pathway in Dual Dynamic Covalent Polymeric Systems

Kinetically controlled self‐assembly is garnering increasing interest in the field of supramolecular polymers and materials, yet examples involving dynamic covalent exchange remain relatively unexplored. Here we report an unexpected dynamic covalent polymeric system whose aqueous self‐assembly pathway is strongly influenced by the kinetics of evaporation of water. The key design is to integrate dual dynamic covalent bonds—including disulfide bonds and boroxine/borate—into a dynamic equilibrium system of monomers, polymers, and materials. This dual dynamic covalent design allows polymer growth and crosslinking to occur with the same spatiotemporal characteristics, governed solely by solvent evaporation. We found that a single building block can assemble into two distinct types of polymeric materials, each characterized by unique crosslinking topologies, orders, solubility, and macroscopic properties. The dual dynamic nature of the materials imparts them with intrinsic reconfigurability, such as interfacial repairability and close‐loop chemical recyclability.