Chiral Self‐Sorting Directed Supramolecular Organic Framework of Imine Cages for Iodine Capture

Abstract Supramolecular organic frameworks (SOFs) with nanotubular pores, assembled through weak non‐covalent interactions, are highly sought‐after for storage, separation, and pollutant capture but are limited. Herein, a SOF assembled with a chiral imine cage is reported by leveraging kinetically driven dynamic covalent chemistry, chiral self‐sorting, and dispersion interactions for efficient iodine capture. The crystallization‐driven synthesis involves a triamine and a racemic mixture of axially chiral dialdehyde equipped in bimesityl (BM) skeleton that undergoes narcissistic chiral self‐sorting to form racemic mixture of homochiral imine cage (BM‐PIC) enantiomers, which result in the SOF (BM‐PIC‐SOF). Notably, excess triamine drives the chiral self‐sorting into heterochiral cages in a favorable solvent. The BM‐PIC‐SOF is templated by solvent molecules and features nanotubular pores (1.4 nm) that are stabilized by non‐covalent interactions, notably, dispersion forces between mesitylene rings. Further, the kinetic crystals of BM‐PIC‐SOF, upon exchange with volatile solvents, undergo single‐crystal‐to‐single‐crystal transformation at high temperature into a thermodynamic polymorph with large structural difference. BM‐PIC‐SOF demonstrates remarkable efficacy in adsorbing iodine not only from vapor (6.0 g.g −1 ) but also from organic (3.88 g.g −1 ) and aqueous mediums (5.01 g g −1 ).