Circularly Polarized Ultraviolet Light‐Activated Asymmetric Photopolymerization for the Synthesis of CPL‐Active Materials

Circularly polarized ultraviolet light (CP‐UVL) offers significant potential for practical applications in asymmetric photocatalysis and photopolymerization. However, the development of CP‐UVL‐active materials has been hindered by their low emission dissymmetry factors (gem). Here, we present a high‐performance CP‐UVL material for asymmetric photopolymerization, achieved through thermodynamic regulation of a chiral supramolecular assembly. The chiral co‐assembled enantiomers, R/S‐BNC/OXD‐7, are synthesized using the naphthylamine derivative R/S‐BNC as the chiral donor and OXD‐7 as the achiral acceptor. Upon annealing at different temperatures, OXD‐7 detaches from the chiral co‐assembly of S‐BNC/OXD‐7 and then self‐assembles into ordered helical nanostructures, exhibiting temperature‐dependent CP‐UVL (λem = 360 nm, with gem up to +0.188). Remarkably, the strong CP‐UVL emission acts as a chiral excitation source, triggering the asymmetric photopolymerization of RM257 (which contains the achiral dye TPABBI and the photoinitiator Irg651), resulting in the generation of blue CPL (λem = 460 nm, gem = −0.072). This study provides a simple yet effective strategy for designing high‐performance CP‐UVL materials for CPL‐induced asymmetric photopolymerization.