Twisting Chiral Aggregation-Induced Emission Macrocycles into a Microhelix with Boosted Circularly Polarized...

The design and assembly of chiral macrocycles remain an underexplored frontier in supramolecular science. In this study, we synthesized a pair of enantiomeric macrocyclic molecules (CP1) through the condensation of chiral cyclohexanediamine with tetraphenylethylene (TPE) dialdehyde. These molecules exhibited remarkable circular dichroism (CD) and circularly polarized luminescence (CPL) properties at the supramolecular level. Through supramolecular assembly in mixed solvent systems, we achieved a rare micron-scale helical structure, exhibiting a high luminescence dissymmetry factor (g_lum) of 0.32-one of the highest values reported to date for macrocyclic self-assemblies. Furthermore, by designing a chiral macrocycle with phenyl spacers (CP2), we revealed that the confinement of macrocycles and restricted internal molecular rotation are critical for achieving high g_lum values and helical structure formation. This work not only advances the design of chiral macrocycles but also provides new insights into the relationship between molecular structure and supramolecular assembly, paving the way for the development of advanced chiral materials with potential applications in optics, sensing, and nanotechnology.