Modulating the radical polymerization behavior of alkenyl boronates via boronate tuning

Boron-containing polymers represent a versatile class of functional materials with growing synthetic importance. While radical polymerization of alkenyl boronate monomers offers a promising route to access these materials, precise control of monomer reactivity remains a fundamental challenge. We report a systematic approach to modulate polymerization pathways through rational boronate group engineering. Strategic manipulation of protecting group steric hinderances enables selective control of polymerization modes, yielding well-defined homopolymers, random copolymers, and alternating copolymers with programmable properties. Electronic tuning of substituents further provides quantitative regulation of polymerization kinetics. These established structure–reactivity relationships offer a robust design framework for developing advanced boronate-functionalized polymeric materials.