Carbon Dioxide Reduction Polymerization toward Multifunctional Unsaturated Polyketones

The carbon dioxide reduction reaction (CO2RR) has emerged as a promising strategy for converting CO2 into value-added chemicals. However, this reaction has rarely been applied in polymer synthesis. Here, we report a tandem CO2 reduction polymerization (CO2RP) that integrates in situ CO2-to-CO conversion with palladium-catalyzed carbonylative polymerization of terminal alkyne and aryl iodide monomers. The developed CO2RP strategy shows excellent catalytic efficiency, affording unsaturated polyynones with high weight-average molecular weights (up to 11,900 g/mol) in high yields (up to 99%). The as-prepared unsaturated polyynones possess outstanding thermal and chemical stability. Moreover, they exhibit prominent aggregation-induced emission (AIE) characteristics and can be applied for highly specific and sensitive detection of ruthenium ions. Notably, the polymer backbones contain reactive alkyne moieties, which enable facile backbone editing and further allow the regulation and enhancement of the refractive index.