Mechanochemical Synthesis of Cationic Graphitic Triazine‐Imidazolium Frameworks

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.