Circularly Polarized Luminescence Reversion and Amplification Promoted by Hydrogen Bonding and Arene–Perfluoroarene Interactions

ABSTRACT The sign regulation of circularly polarized luminescence (CPL) signals and the amplification of dissymmetry factors are highly desirable yet remain challenging to design due to the complex interplay between molecular structure and supramolecular assembly. Here, we employed two chiral binaphthyl derivatives, namely an ester ( R / S ‐1 ) and an amide ( R / S ‐2 ), to co‐assemble with octafluoronaphthalene (OFN) through arene–perfluoroarene (AP) interactions, yielding R / S ‐1/OFN and R / S ‐2/OFN . Both R / S ‐1 and R / S ‐2 showed clear excimer emission in the aggregated state. However, R / S ‐1 displayed relatively weak CPL signals, whereas R / S ‐2 exhibited a stronger CPL response with the opposite sign. More importantly, the co‐assembly process with OFN through AP interactions led to a marked enhancement of CPL in both systems, with the luminescence dissymmetry factor ( g lum ) of about 0.016 for R / S ‐1/OFN and 0.038 for R / S ‐2/OFN . This work highlights a simple yet effective strategy to control CPL sign and intensity through subtle chemical modification and hetero‐assembly driven by AP interactions, and provides a general approach for designing high‐performance chiroptical materials.