Sulfur(VI) Fluoride Exchange Chemistry in Polymer Functionalization: Post-Polymerization Modification, Interface Engineering, and Biopolymer Conjugation.

Sulfur(VI) fluoride exchange (SuFEx) chemistry is a powerful click reaction for modular synthesis, distinguished by high chemoselectivity, broad functional-group tolerance and the formation of robust sulfur(VI)-based linkages. These attributes are particularly valuable for polymer functionalization, as S(VI)-F handles on either the polymer or the modifier enable covalent coupling under controlled conditions. This review spans SuFEx-mediated post-polymerization modification and architectural control of synthetic polymers, surface, interfacial and porous-material functionalization, and SuFEx-based conjugation and covalent capture in natural and sequence-defined biopolymers. Across these contexts, we compare the advantages, supporting mechanistic and analytical evidence, current limitations and future opportunities of SuFEx-enabled polymer functionalization.