Mechanochemical Synthesis of Cationic Graphitic Triazine‐Imidazolium Frameworks

Abstract Although emerging ionic covalent organic frameworks (COFs) offer structural adaptability and diverse functionality, their synthesis is still limited by a few compatible reactions, scarce monomer options, scalability challenges, and sustainability demands. Herein, a mechanochemical approach is reported to construct crystalline cationic graphitic triazine‐imidazolium frameworks through nucleophilic aromatic substitution, utilizing low‐cost industrial feedstocks. This solvent‐free strategy enables rapid and scalable assembly of cationic frameworks with graphite‐like crystallinity and varying interlayer spacing. The resulting materials demonstrate tunable optical properties and excellent iodine capture performance, with cost‐effectiveness analyses proving their real‐world viability. The breakthrough methodology expands the synthetic toolbox for ionic COFs and pioneers mechanochemistry as a green approach in developing charged framework materials.