Chirality‐Induced Split Personality in Polymer with Intrinsic Microporosity‐Based Artificial Ion Channels

Abstract The construction of artificial transmembrane ion channels using polymers has emerged as a promising research avenue in membrane transport. In this study, we have designed and synthesized an intriguing class of intrinsically microporous chiral polyimides (PIM‐PIs) employing trans / cis ‐1,2‐diaminocyclohexanes (DACH) as structural building blocks. Remarkably, these chiral PIM‐PIs exhibit distinct configurations, leading to contrasting ion transport properties. The cis‐DACH‐derived chiral polymer 1 demonstrates the hitherto highest Li + transport activity (>100 pS), along with exceptionally high selectivity ratios for Li + /Na + (17.1) and Li + /K + (21.8). In contrast, chiral polymers 2a and 2b , synthesized from (1 R ,2 R )‐DACH and (1 S ,2 S )‐DACH, respectively, showcase pronounced anion transport capabilities and a remarkably high Cl − /K + selectivity ratio of 17.6. This work introduces a multifunctional, chiral PIM‐based artificial ion channel system with a “split personality” governed by its chiral constituents. It represents the first application of chiral polymers in transmembrane transport, inspiring innovative design strategies for developing polymer‐based artificial ion channels.