Chirality-Controllable Self-Sorting in Macrocyclic Supramolecular Assemblies: Homochiral and Heterochiral 1D Architectures.

Chiral self-sorting, including both narcissistic and social self-sorting, can generate homochiral and heterochiral supramolecular assemblies, respectively. However, achieving control over both pathways through molecular design remains challenging. Herein, we designed a series of macrocyclic pillar[5]arene derivatives with linear chains that thread into the cavities of adjacent molecules in the crystal, forming 1D superstructures. By varying the rigidity of these linear chains, we discovered that the rigidity dictated chiral preference: rigid chains induced homochiral arrangements, whereas flexible chains favored heterochiral arrangements. Mechanistically, the close packing of adjacent pillar[5]arenes through host-guest supramolecular system played a crucial role in controlling the chiral sequence.