Controlled Assembly of [3+6] and [4+8] Porous Organic Cages for Rapid Removal of Iodide from Water

Comprehensive Summary Research into controlling the self‐assembly of discrete porous organic cages (POCs) with specific geometries and functions is difficult, but important for understanding their structure‐property relationship, as well as self‐assembly behavior in supramolecular chemistry. Herein, we report the self‐assembly of two POCs based on the same tetraformyl‐functionalized calix[4]resorcinarene (C4RACHO) and 2,4‐diaminophenol dihydrochloride (DAP) organic building blocks, including a [3+6] triangular prism ( CPOC‐201‐OH ) and a [4+8] square prism ( CPOC‐401‐OH ), as determined by single X‐ray crystallographic analysis. Both POCs exhibit large intrinsic cavities, rich oxygen sites, and high porosity with Brunauer–Emmett–Teller (BET) specific surface areas up to 966 m 2 ·g –1 . Owing to such virtues, both cages can effectively capture iodine in aqueous media with removal rate > 99% within 2 min.