Discrete Chiral Metallacycle‐Based Membrane for Highly Efficient Enantioseparation

Abstract Macrocyclic membranes provide a promising solution for efficient enantioseparation, but the synthesis of discrete chiral macrocyclic materials remains a formidable challenge. In this study, well‐defined chiral metallacycles 1 and 2 , featuring intrinsic bis‐thiourea derivative, are prepared via the coordination‐driven self‐assembly by combining metallic precursor 4 , 5 , and organic precursor 3 . Subsequently, varying amounts of metallacycle 1 are readily integrated into polysulfone to generate the chiral metallacycle‐based enantioselective membranes (MNM‐10, 20, 30) via the solvent evaporation method. The MNM‐20 membrane demonstrates highly efficient enantioseparation (up to 100%) for racemic 1‐phenylethanol, 1‐phenylethylamine, and methyl mandelate with superior antifouling performance. The high enantioselectivity is confirmed through ionic current tests, thermodynamic data, and theoretical simulations. It is notable that the integration of MNM‐20 into tubular membrane modules resulted in the maintenance of its high enantioselectivity and the achievement of a flux enhancement 16 times higher than that obtained through the permeation method. This work provides a foundation for the development of chiral membranes for separating enantiomers and biomolecules.