Multicomponent tandem polymerization of alkynes, CO2, alkyl bromide, and thiol toward functional poly(β-thioacrylate)s

Abstract

The direct conversion of carbon dioxide (CO₂) into value-added polymeric materials has garnered considerable research interest in recent decades. Multicomponent tandem polymerization (MCTP), as an emerging synthetic strategy, demonstrates exceptional efficiency in constructing functional polymers. Nevertheless, CO₂-involved MCTP systems have been rarely reported. Herein, we developed a one-pot MCTP involving CO₂, alkynes, alkyl bromide, and thiol, enabling the efficient transformation of CO₂ into structurally well-defined regioregular polymers. The polymerization process mediated by Ag₂WO₄ and Cs₂CO₃ under ambient pressure in N,N-dimethylacetamide upon heating produced four soluble poly(β-thioacrylate)s with high weight-average molecular weights (up to 11 500 g mol⁻¹) and Z-stereoregularities (up to 84%). Notably, the tetraphenylethene-containing polymer exhibited aggregation-induced emission features, demonstrating its potential as a dopant in liquid crystalline polymer networks. The resulting film displayed circularly polarized luminescence properties with an exceptional luminescence dissymmetry factor of −0.88. Intriguingly, the polymer/polyamide 6 (PA6) composites manifested room-temperature phosphorescence featuring long emission lifetimes up to 510 ms. Furthermore, the polymers could be post-modified by the thiol–ene click reaction to produce sulfur-rich polymers. This work provides a robust platform for converting CO₂ into stereoregular polymeric materials with tailorable photophysical properties, offering promising applications in advanced optoelectronic materials and sustainable technologies.