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 (g_em). Here, we present a high-performance CP-UVL material for asymmetric photopolymerization, achieved through thermodynamic regulation of a chiral supramolecular assembly. The chiral coassembled 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 coassembly of S-BNC/OXD-7 and then self-assembles into ordered helical nanostructures, exhibiting temperature-dependent CP-UVL (λ_em = 360 nm, with g_em 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 (λ_em= 460 nm, g_em = -0.072). This study provides a simple yet effective strategy for designing high-performance CP-UVL materials for CPL-induced asymmetric photopolymerization.