Metal-organic cages and capsules exhibit space-specific functions based on their discrete hollow structures. To acquire enzyme-like asymmetric or intricate structures, they have been modified by desymmetrization with two or more different ligands. There is a need to establish new strategies that can desymmetrize structures in a simple way using only one type of ligand, which is different from the mixed-ligand approach. In this study, a strategy was developed to form interconvertible stereoisomers using the unsymmetric macrocyclic ligand benzimidazole[3]arene. Single-crystal X-ray diffraction analysis revealed that the isomers assembled with silver tetrafluoroborate afforded a conformationally heteroleptic Ag

Intricate Low-Symmetry Ag6L4 Capsules Formed by Anion-Templated Self-Assembly of the Stereoisomers of an Unsymmetric Ligand