Abstract
Conventional topochemical photopolymerization reactions occur exclusively in precisely-engineered photoactive crystalline states, which often produces high-insoluble polymers. To mitigate this, here, we report the mechanoactivation of photostable styryldipyrylium-based monomers, which results in their amorphization-enabled solid-state photopolymerization and produces soluble and processable amorphous polymers. A combination of solid-state nuclear magnetic resonance, X-ray diffraction, and absorption/fluorescence spectroscopy reveals the crucial role of a mechanically-disordered monomer phase in yielding polymers via photo-induced [2 + 2] cycloaddition reaction. Hence, mechanoactivation and amorphization can expand the scope of topochemical polymerization conditions to open up opportunities for generating polymers that are otherwise difficult to synthesize and analyze.