Abstract

The synthesis and application of multifunctional diazirines as efficient precursors for the on-demand generation of carbenes is demonstrated. While small-molecule multifunctional diazirines have seen significant application in fields such as plastic compatibilization and photopatterning, the synthesis and polymerization of diazirine-based monomers is unexplored. This study focuses on the preparation of diazirine-containing polyacrylates and polymethacrylates through controlled radical polymerization. Both reversible addition–fragmentation chain-transfer (RAFT) polymerization and atom-transfer radical polymerization (ATRP) techniques are shown to be efficient for preparing polymers with targeted diazirine contents and degrees of polymerization. The resulting polymers represent a versatile cross-linking platform through reaction with ubiquitous C–H bonds. This stability and synthetic accessibility underscore the potential of diazirine-containing polymers for efficient cross-linking and functionalization strategies.