Abstract

AbstractPhoto‐controlled polymerizations are attractive to tailor macromolecules of complex compositions with spatiotemporal regulation. In this work, with a convenient synthesis for trifluorovinyl boronic ester (TFVB), we report a light‐driven organocatalyzed copolymerization of vinyl monomers and TFVB for the first time, which enabled the controlled synthesis of a variety of hybrid fluorine/boron polymers with low dispersities and good chain‐end fidelity. The good behaviors of “ON/OFF” switch, chain‐extension polymerizations and post‐modifications further highlight the versatility and reliability of this copolymerization. Furthermore, we demonstrate that the combination of fluorine and boron could furnish copolymer electrolytes of high lithium‐ion transference number (up to 0.83), bringing new opportunities of engineering high‐performance materials for energy storage purposes.

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