Photo‐Decrypted Narcissistic Self‐Sorting in Chirality‐Driven Supramolecular System

Chirality-driven self-assembly is crucial in biological systems, but achieving precise control over chiral narcissistic or social self-sorting as well as the distinction between them remains a major challenge in multicomponent supramolecular systems. To investigate chirality-driven self-assembly, two classes of chiral building blocks, photo-responsive (cinnamic glutamide derivative, L/D-CG) and fluorescent molecules (dansyl glutamide derivative, L/D-DNSG), were designed and integrated into homochiral systems (L-CG/L-DNSG or D-CG/D-DNSG) and heterochiral systems (L-CG/D-DNSG or D-CG/L-DNSG). Either homo- or heterochiral systems could form organogels with fibrous structures. Upon photoirradiation, the homochiral systems remained stable, whereas the heterochiral systems underwent a significant transformation from uniform organogels to suspensions, in which nanokebab structures appeared. The results demonstrate that social self-sorting dominates in the homochiral systems while narcissistic self-sorting prevails in the heterochiral systems. Remarkably, the difference between homochiral and heterochiral systems is magnified through photodimerization. Various characterizations and simulations unveil the underlying homo- and heterochiral interactions that drive narcissistic self-sorting from the molecular to hierarchical nanoscale levels. This work decrypts the narcissistic or social self-sorting behavior in chirality-driven supramolecular systems through photoirradiation and provides a new perspective for understanding the regulation of chiral-driven functions in biological or material systems.