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.