Dynamic Stereochemistry of M8Pd6 Supramolecular Cages Based on Metal‐Center Lability for Differential Chiral Induction, Resolution, and Recognition

Abstract A series of isostructural supramolecular cages with a rhombic dodecahedron shape have been assembled with distinct metal‐coordination lability (M 8 Pd 6 ‐MOC‐16, M=Ru 2+ , Fe 2+ , Ni 2+ , Zn 2+ ). The chirality transfer between metal centers generally imposes homochirality on individual cages to enable solvent‐dependent spontaneous resolution of Δ 8 / Λ 8 −M 8 Pd 6 enantiomers; however, their distinguishable stereochemical dynamics manifests differential chiral phenomena governed by the cage stability following the order Ru 8 Pd 6 > Ni 8 Pd 6 > Fe 8 Pd 6 > Zn 8 Pd 6 . The highly labile Zn centers endow the Zn 8 Pd 6 cage with conformational flexibility and deformation, enabling intrigue chiral‐ Δ 8 / Λ 8 −Zn 8 Pd 6 to meso‐ Δ 4 Λ 4 −Zn 8 Pd 6 transition induced by anions. The cage stabilization effect differs from inert Ru 2+ , metastable Fe 2+ /Ni 2+ , and labile Zn 2+ , resulting in different chiral‐guest induction. Strikingly, solvent‐mediated host–guest interactions have been revealed for Δ 8 / Λ 8 −(Ru/Ni/Fe) 8 Pd 6 cages to discriminate the chiral recognition of the guests with opposite chirality. These results demonstrate a versatile procedure to control the stereochemistry of metal‐organic cages based on the dynamic metal centers, thus providing guidance to maneuver cage chirality at a supramolecular level by virtue of the solvent, anion, and guest to benefit practical applications.