Synergistic d-π Conjugation and Thermal Stability Enable Efficient High-Temperature Photoinduced Olefin Polymerization in Metallocene–Organic Semiconductor Hybrids

Achieving efficient and thermally stable high-temperature olefin polymerization remains a critical challenge for polyolefin elastomer (POE) synthesis. Herein, we construct metallocene–organic semiconductor hybrid photocatalysts, Cp 2 ZrCl 2 @PM6 and Cp 2 ZrCl 2 @Y6, via stacking and d-π conjugation. Comprehensive experimental and theoretical investigations reveal that PM6 forms strong d-π orbital hybridization with the Zr center across a broad energy range, accompanied by robust interfacial binding (−6.445 eV) and efficient charge transfer. In contrast, Y6 exhibits weaker d-π conjugation and inferior thermal stability, melting into disorder at 150 °C while PM6 retains ordered π-stacking. Consequently, the Cp 2 ZrCl 2 @PM6 system achieves 10.8-fold higher activity than pristine Cp 2 ZrCl 2 and 2.25-fold higher than Cp 2 ZrCl 2 @Y6, enabling industrial-scale ethylene/1-octene copolymerization at 423 K. The resulting POE exhibits superior mechanical properties and excellent film processability, validating the practical potential of this synergistic strategy.