Covalent Organic Framework Mediated Polymerization for Multifunctional Applications.

Polymers constitute indispensable functional components across energy, environmental, and biomedical applications, yet precise control over their primary and higher-order structures remains a core challenge. Covalent organic frameworks (COFs), a class of crystalline porous materials featuring designable topologies, tunable chemical compositions, and permanent ordered pore channels, provide a molecular-level platform for monomer polymerization through their inherent pore confinement and interfacial synergistic effects. This review systematically summarizes two principal strategies for COF-mediated polymerization. COFs can serve as confined nanoreactors to regulate polymer chain growth, while addressable reactive sites within their skeletons can be exploited to construct polymer-cross-linked networks. This review elucidates the corresponding polymerization mechanisms, clarifies material design principles through representative examples, and expands the application scope of COFs. Finally, we outline future challenges and opportunities in this field, encompassing precision design, polymerization mechanism, and scalable applications.