Design and Enantioresolution of Homochiral Fe(II)-Pd(II) Coordination Cages from Stereolabile Metalloligands: Stereochemical Stability and Enantioselective Separation.

The stereochemistry of chiral-at-metal complexes is much more abundant, albeit complicated, than chiral-at-carbon compounds, but how to make use of stereolabile metal-centers remains a formidable challenge due to the highly versatile coordination geometry of metal ions and racemization/epimerization problem. We demonstrate herein a stepwise assembly of configurationally stable [Pd(FeL)] (Δ/Λ-MOCs-42) homochiral octahedral cages from unstable D-symmetry tris-chelate-Fe type metalloligands via strong face-directed stereochemical coupling and facile chiral-induced resolution processes based on stereodifferentiating host-guest dynamics. Kinetic studies reveal that the dissociation rate of MOC-42 cages is 100-fold slower than that of Fe-metalloligands and the racemization is effectively inhibited, making the cages retain their chirality over extended periods of time (>5 months) at room temperature. Recyclable enantioseparation of atropisomeric compounds has been successfully achieved, giving up to 88% ee.