Homocoupling of Fluoroarenes: A Mechanochemical Approach Toward Porous Conjugated Scaffolds Construction

The knitting of fluoroarenes represents an attractive technique to afford high-quality conjugated porous networks (CPNs) with unique features and applications in the field of separation, catalysis, and energy storage, harnessing abundant fluoroarene derivatives, tunable residual fluorine content in the scaffolds, and permeant micropores derived from C-F bond cleavage. However, limited approaches could enable efficient fluoroarene polymerization due to the strong dissociation energy of the C-F bonds. Herein, the construction of fluorinated CPNs was achieved via a facile mechanochemistry-driven procedure in the presence of metal catalysts under ambient and neat conditions. The homocoupling of diverse fluoroarenes (perfluorinated arenes, fluorinated aromatic nitriles/aldehydes/carboxylic acids, and fluoroarenes with triazine/phosphine/boron cores) via C-F bond cleavage and C-C bond construction was promoted by the formation of transition metal fluorides via the on-surface Ullmann-type polymerization. The as-afforded CPNs were featured by extensive conjugation, large surface area, permeant porosity, and abundant fluorine/heteroatoms doping, possessing attractive electrochemical performance.