Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer Separation

Cage‐like metal–organic frameworks (MOFs) are promising for hexane isomer separation, but their aperture sizes are difficult to control precisely. Herein, a molecular valve strategy is proposed to fine‐tune the aperture of cage‐like MOFs, thereby enhancing their separation performance for hexane isomers. Three novel isostructural cage‐like MOFs, namely Cu‐MO₄‐TPA, are synthesized using different oxometallate anions (MO₄²⁻, M = Cr, Mo, and W) and the ligand tri(pyridin‐4‐yl)amine (TPA). The different oxometallate anions induce varying degrees of twisting in the TPA ligand, leading to sub‐angstrom tuning in the aperture size of the MOFs. The materials can separate hexane isomers based on their degree of branching, with the smallest aperture material (Cu‐MoO₄‐TPA) showing molecular sieving of di‐branched isomers. Adsorption isotherms, kinetic, and breakthrough measurements, Monte Carlo, and density functional theory calculations confirm the aperture size differences result in superior separation of hexane isomers by molecular sieving on Cu‐MoO₄‐TPA. The results demonstrate the effectiveness of molecular valve strategy for fine‐tuning MOF aperture size for selective separation applications.