Dynamic Stereochemistry of M<sub>8</sub>Pd<sub>6</sub> Supramolecular Cages Based on Metal‐Center Lability for Differential Chiral Induction, Resolution, and Recognition
Yin‐Hui Huang, Yu‐Lin Lu, Xiaodong Zhang, Chen‐Hui Liu, Jia Ruan, Yuhan Qin, Zhong‐Min Cao, Ji‐Jun Jiang, Hai‐Sen Xu, Cheng‐Yong Su
Abstract
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.