Continuous Metal–Organic Polyhedral Membranes Derived from Intermolecular Transitions for Precise Gas Separation

Abstract As an emerging class of porous solid materials, metal–organic polyhedra (MOPs), possess inherent porosity and excellent solvent processability, making them highly promising candidates for membrane separation applications. However, the development of continuous and structurally stable MOP‐based membranes remains a significant challenge due to the weak noncovalent intermolecular interactions. Herein, an intermolecular transitions strategy is implemented to enhance the intermolecular interactions within MOPs molecules. By transforming unstable intermolecular hydrogen bonds into stable covalent bonds, the continuous metal–organic polyhedral (cMOP) film is successfully constructed. The robust channel‐guest interaction between the angstrom‐scale channels and CO ₂ molecules endows the prepared cMOP composite membrane with a remarkable CO ₂ /N ₂ selectivity of 38 at 1 bar, underscoring the feasibility of employing MOPs to construct efficient continuous angstrom‐scale channels for precise gas separation. These findings offer valuable theoretical insights into the continuous assembly of metal–organic porous materials, which is promising for the fabrication of membranes for efficient gas separations.