Mechanistic Insights Into the Solid‐State Redox Reactions: Role of Organic Piezoelectric Materials

ABSTRACT

Mechanochemistry has gained tremendous recent attention because it combines sustainability with the ability to access unique reaction pathways and materials while offering practical advantages for efficient and scalable chemical synthesis. However, predicting solid‐state transformations from mechanical energy remains a formidable challenge, as the current mechanistic models are insufficient. While solid‐state electrocatalytic reactions in the presence of inorganic piezoelectric materials have been demonstrated recently, the ability of piezoelectric organic solids, which possess an order of magnitude lower piezoelectric coefficients, remain completely unexplored. Here, using different crystalline forms, we demonstrate that under ball‐milling, non‐centrosymmetric organic crystals generate piezoelectric potentials that are sufficient to drive a range of redox bond‐forming reactions, including C─B, C─S, C─Se, C─C, and C─P couplings. To further evaluate the role of piezoelectricity, we compared chemically identical crystal forms of a compound, differing only in symmetry: Non‐centrosymmetric crystals are highly reactive, whereas centrosymmetric counterparts remain largely inert. These findings reveal crystal symmetry as a previously unrecognized determinant of chemical function and identify organic piezoelectric solids as active energy‐transduction media for chemical synthesis. More broadly, this work provides a framework for designing self‐powered chemical systems that directly couple mechanical energy harvesting with molecular transformation.