Controlling the Chirality of Metallo‐Cages by Manipulating the Stereochemistry of the Metal Centers

Precise control over the chirality of metallo‐cages by manipulating the stereochemistry of metal centers is important in many practical applications, but is extremely challenging. In this study, two isostructural metallo‐cuboctahedra ( 1 ‐Zn II 12 L1 8 and 2 ‐Cd II 12 L1 8 ) have been assembled using ligand L1 and two kinds of metal ions (Zn II and Cd II ) with similar coordination lability. The chiral‐induction by the same guests ( D ‐/ L ‐camphorsulfonate, D ‐/ L ‐SCS) results in a completely opposing stereochemical output of 1 and 2 : D ‐SCS induced host–guest complex of [ D ‐SCS⊂Δ 12 – 1 ] and [ D ‐SCS⊂Λ 12 – 2 ], respectively, with reverse handedness. The distinct stereochemical configuration of metallo‐cuboctahedra can be manipulated by participant metal ions that exhibit similar dynamics. Furthermore, a subtle variation of the ligand peripheral substituent group facilitates spontaneous resolution of metallo‐cuboctahedra 3 ‐Zn II 12 L2 8 from a racemic mixture as ( R 24 , Λ 12 )‐ 3 /( S 24 , Δ 12 )‐ 3 enantiopure entities. The dynamic stereochemistry of M II 12 L 8 cuboctahedra described in this work allows a chiral manipulation based on the nature of metal centers and ligands, enabling the design and control of the chirality of metallo‐cages.