Regioisomer-Dependent Supramolecular Assembly of Coumarin Derivatives for Wavelength-Dependent Blue and Near-Infrared Circularly Polarized Luminescence.

Supramolecular assemblies exhibiting circularly polarized luminescence (CPL) are attractive candidates for advanced photonic and optoelectronic materials. However, precise regulation of CPL output across distinct wavelength regions remains challenging, particularly in systems that require the programmable integration of molecular structure, supramolecular chirality, energy transfer, and external-stimulus responsiveness. Herein, we report two chiral coumarin-based cholesterol amide derivatives that exhibit striking regioisomer-dependent assembly behavior and CPL properties. Notably, CHC-1 selectively forms long-range ordered chiral nanofibers in both polar and nonpolar solvents, giving rise to pronounced supramolecular chirality together with strong blue CPL activity. Single-crystal analysis and theoretical calculations jointly demonstrate that subtle structural isomerism has a pronounced impact on assembly activity. Moreover, co-assembly of CHC-1 with thioflavin T affords strong green CPL emission through efficient energy transfer. Furthermore, incorporation of the photoisomerizable spiropyran allows photoresponsive modulation of wavelength-dependent CPL behavior. Benefiting from the photoisomerization of spiropyran, the co-assembled gels show distinct near-infrared CPL emission. This work establishes a versatile strategy for constructing wavelength-dependent, multi-mode CPL supramolecular systems and highlights how structurally programmed assembly can be leveraged to regulate chiroptical properties in multi-component materials.