Force‐Induced Selective Carbon‐Carbon Bond Cleavage in Mechanoresponsive Topochemical Polymers

Abstract Mechanoresponsive polymeric materials that respond to mechanical deformation are highly valued for their potential in sensors, degradation studies, and optoelectronics. However, direct visualization and detection of these responses remain significant obstacles. In this study, novel mechanoresponsive polybiidenedionediyl (PBIT) derivative topochemical polymers are developed that depolymerize under mechanical forces, exhibiting a distinct and irreversible color change in response to grinding, milling, and compression. This color change is attributed to the alteration of polymer backbone conjugation during elongated Carbon‐Carbon (C─C) single bond cleavage. Quantum chemical pulling simulations on PBIT polymers reveals a force range of 4.3–5.0 nN associated with the selective cleavage of elongated C─C single bonds. This force range is comparable to that observed for typical homolytic mechanophores, supporting the mechanistic interpretation of homolytic bond scission under mechanical stress. C─C bond cleavage kinetic studies of PBIT under compression indicates that strong interchain interactions significantly increase the pressure needed to cleave the elongated C─C bonds. Additionally, PBIT polymer thin films are composited with polydimethylsiloxane to create free‐standing and robust thin films, which can serve as ink‐free and rewritable paper for writing and stress visualization applications. This advancement opens new possibilities for utilizing crystalline and brittle topochemical polymers in practical applications.