Eugenol-based optically active helical polymers: from controlled synthesis to post-polymerization modification and chiral recognition

• • Helix-selective living polymerization of achiral eugenol-based diazo acetate using chiral Pd/Wei-Phos catalyst yields helical polycarbenes with controlled molecular weight and narrow dispersity (Đ), enabling precise tuning of polymer properties for advanced applications. • • Post-polymerization thiol-ene click chemistry achieves >99% conversion for introducing carboxyl, ester, ketone, and diol groups, allowing versatile functionalization without compromising helical structure. • • PETMP cross-linked eugenol-based polycarbene films exhibit tunable tensile strength up to 15 MPa by adjusting polymerization degree and cross-linking density, offering mechanically robust materials for chiral separation. • • Cross-linked films demonstrate chiral recognition capability with enantiomeric excess (ee) up to 96% for various chiral alcohols, providing a sustainable alternative for enantioseparation processes.