Shape‐Selective Molecular Separations Enabled by Rigid and Interconnected Confinements Engineered in Conjugated Microporous Polymer Membranes

Separating molecules with similar sizes but different shapes is essential yet challenging. Here, conjugated microporous polymer (CMP) membranes with narrowly distributed network pores are prepared by diffusion-modulated electropolymerization. This approach precisely controls the monomer diffusion and coupling processes, regulating the crosslinking degree to prevent broad aggregate pores and microporous defects. By altering carbazole-based backbones, pore size and pore connectivity are adjusted. The rigid and interconnected confinements restrict molecular rotation and vibration, enforcing consistent shapes and orientations. This enables the separation of solute molecules (≈1000 g mol^-1) with linear and bulky shapes, achieving separation factors of up to 134. When pore size is reduced to angstrom scale (≈5 Å), molecular shape significantly influences organic liquid transport. The CMP membranes demonstrate all-liquid phase separation of linear/branched alkane isomers (<100 g mol^-1), enriching hexane to 63.35 mole% from equimolar isomer mixture and achieving permeance orders of magnitude higher than those of state-of-the-art membranes.