Rationalizing the formation of porosity in mechanochemically-synthesized polymers.

In this study, we present a matrix of 144 mechanochemically-synthesized polymers. All polymers were constructed by the solvent-free Friedel-Crafts polymerization approach, employing 16 aryl-containing monomers and 9 halide-containing linkers, which were processed in a high-speed ball mill. This Polymer Matrix was utilized to investigate the origin of porosity in Friedel-Crafts polymerizations in detail. By examining the physical state, molecular size, geometry, flexibility, and electronic structure of the utilized monomers and linkers, we identified the most important factors influencing the formation of porous polymers. We analyzed the significance of these factors for both monomers and linkers based on the yield and specific surface area of the generated polymers. Our in-depth evaluation serves as a benchmark study for future targeted design of porous polymers by the facile and sustainable concept of mechanochemistry.