Encoding Supramolecular Chiral Self‐Assembly with Photo‐Controlled Circularly Polarized Luminescence by Overcrowded Alkene‐Based Bis‐PBI Modulators

Abstract Developing photoresponsive circularly polarized luminescence (CPL) materials is an essential step for biosensing and biomedical applications. However, fabricating CPL assemblies rooted in the chirality amplification and transmission of the molecular building blocks, which simultaneously show photo‐controllable CPL signals, remains challenging. Herein, a molecular building block containing an overcrowded‐alkene core and bis‐ PBI ( MPBI ) was designed. Importantly, the enantiopure MPBI can self‐assemble into well‐organized nanofibers via π‐π stacking interactions and enable the transmission of the intrinsic chirality, providing opposite CPL signals. The photoisomerization of MPBI induced a transformation from nanofibers to discrete nanospheres, accompanied by a gradually decreased CPL signal. The results demonstrated the development of photo‐controllable CPL materials from the assembly of chiral MPBI , which provides an alternatively facile strategy to fabricate CPL‐active materials and would offer opportunities for future biosensing and biomedical applications.