Barbier Self-Condensing Ketyl Polymerization-Induced Emission: A Polarity Reversal Approach to Reversed Polymerizability.

Carbon-carbon bond formation through polarity reversal ketyl radical anion coupling of carbonyls has inspired new reaction modes to this cornerstone carbonyl group and played significant roles in organic chemistry. The introduction of this resplendent polarity reversal ketyl strategy into polymer chemistry will inspire new polymerization mode with unpredicted discoveries. Here we show the successful introduction of polarity reversal ketyl approach to polymer chemistry to realize self-condensing ketyl polymerization with polymerization-induced emission. In this polarity reversal approach, it exhibits intriguing reversed polymerizability, where traditional excellent leaving groups are not suitable for polymerization but challenging polymerizations involving the cleavage of challenging C-F and C-CF bonds are realized under mild Barbier conditions. This polarity reversal approach enables the polymer chemistry with polarity reversal ketyl mode, opens up a new avenue toward the polymerization of challenging C-X bonds under mild conditions, and sparks design inspiration of new reaction, polymerization, and functional polymer.