Fast Synthesis of Olefin-Linked Covalent Organic Frameworks via Supercritically Solvothermal Polymerization

Covalent organic frameworks (COFs) are newly emerging yet rapidly developed porous crystalline polymeric materials, which feature topological designability, structural diversity, and porosity tunability. However, most of the reported COFs hitherto are prepared by a solvothermal method, which needs a long reaction time, especially for the olefin-linked COFs, which hinders their practical applications. Herein, we report the fast growth of olefin-linked COFs synthesized by the supercritical solvothermal method under supercritical carbon dioxide conditions. Via optimization of the reaction conditions, olefin-linked COFs are prepared within 6 h, which is period much shorter than that of the traditional solvothermal method. The as-obtained COFs feature two distinct morphologies, namely, spherical and rod-like. Interestingly, the rod-like crystal shows polarized light extinction and rebrightening phenomena, indicating the high crystallinity. After being doped with I₂, the obtained I₂@COF_TMT-PA shows a Hall mobility of 1.94 cm² V^-1 S^-1, indicating its potential applications in optoelectronics. This work expands the application of the supercritically solvothermal method to the fast growth of olefin-linked COFs and solves a long-standing challenge in chemical science, which opens up opportunities for basic research as well as practical applications of olefin-linked COFs and other polymeric materials.