Chiral Polar Bifunctional Polyimide Enantiomers for Asymmetric Photo‐ and Piezo‐Catalysis

Chiral catalysts for asymmetric catalysis represent a crucial research focus in chemistry and materials science. However, a few cases about chiral-dependent photocatalysts primarily focus on plasmonic noble metals. Particularly, developing chiral nano-catalysts that can be driven by mechanical energy remains in the blank stage. Herein, organic polymer-based enantiomers, chiral polar polyimide (PI) microspheric nano-assembly are synthesized as novel bifunctional catalysts for asymmetric photocatalysis and piezocatalysis. The PI catalyst enantiomers present enantioselectivity towards left- and right-circularly polarized light, demonstrating chiral-dependent H₂O₂ photoproduction. Interestingly, enantioselectivity of the catalyst reverses under irradiation of different bands, presenting tunability in the interaction between chiral catalysts and circularly polarized light. For the first time, enantioselective piezocatalytic behavior is demonstrated by the chiral polar PI catalysts. They show remarkable chiral preference for asymmetric Diels-Alder reaction and enantioselective conversion of tyrosine substrates under ultrasonic vibration. The findings provide a new perspective into exploring metal-free chiral catalysts and their asymmetric catalysis applications across multiple energy forms.