Lützen and co-workers exploited flexible BINOL-based bis(pyridine) ligands to assemble enantiopure endo-or exofunctionalized M 6 L 12 -type or M 12 L 24 -type cages (MOC-8-9), respectively, based on the position of the substitution on the BINOL core (with the exception of the edge-directed construction of chiral M 4 L 6 tetrahedral cages). 72 A subsequent investigation was undertaken to examine the analogous flexible BINOL-based ligand assembly with Pd II , with the anticipation of obtaining a homochiral Pd2L4 complex, However, instead, chiral Pd4L8 (MOC-10) assembly was obtained. Single-crystal X-ray diffraction analysis revealed a unique stretched tetrahedron structure, where four Pd(II) ions occupy the vertices. Among the eight ligands, four exhibit a twisted C-shaped configuration, while the other four adopt a W-shaped configuration. The unique arrangement of the assembly led to the formation of three cavities: two peripheral cavities accommodated two BF4 anions, while a central cavity with a hydrophilic nature was occupied by acetonitrile molecules (Figure ). Furthermore, a series of chiral metallacycles and cages were successfully synthesized by Stang and co-workers employing a chiral BINOL-based Recently, Nitschke group reported an enantiopure Fe4L6 cage (MOC-11), where the stereochemistry is defined by the incorporation of a chiral formylpyridine subcomponent (Figure ). Subsequent fullerene (C60) encapsulation and chemo-, regio-and enantio-selective Diels-Alder cycloaddition with the cage's anthracene panels resulted in the inherently chiral functionalization patterns of homo-and hetero-substituted C60 analogs.