The copper-catalyzed Glaser coupling is conducted mechanochemically, with the milling balls and vessels being the catalyst. Thus, neither catalyst powders nor soluble catalyst salts are required. Substituting Cu 0 milling tools by copper alloys not only increases the yield of the reaction, but also greatly reduces abrasion, and in turn increases catalyst long-term stability and reusability. Tracking the reaction by Raman spectroscopy allows to identify the active intermediate directly on the milling ball surface and propose a reaction mechanism.

Elemental copper can be utilized to generate C−C bonds in order to synthesize nanographenes in a mechanochemical environment. Utilizing the solvent-free environment of a ball mill, we present a facile and highly sustainable concept for the internal C−C coupling in oligo-phenyls on the example of triphenylene and extend it to the transformation of hexaphenylbenzene into hexa-peri-hexabenzocoronene as a benchmark nanographene.

An oxidative polymerization reaction was brought into the solvent-free environment of a ball mill, yielding a porous polymer with a defined structure and high surface area.