Current approaches to the discovery of mechanochemical reactions in polymers are limited by the interconnection of the zero-force and force-modified potential energy surfaces since most mechanochemical reactions are force-biased thermal reactions. Here, carbamoyloximes are developed as a mechanophore class in which the mechanochemical reaction rates counterintuitively increase together with the thermal stability. All carbamoyloxime mechanophores undergo force-induced homolytic bond scission at the N-O bond, and their mechanochemical scission rate increases with the degree of substitution on the α-substituent. Yet, carbamoylaldoximes react to both heat and light with a pericyclic syn elimination, while carbamoylketoximes undergo thermal decomposition at high temperature and photochemical homolytic scission only from the triplet state. Thereby, the mechanochemical and thermal reaction trajectories are separated, and the thermal stability increases alongside the mechanochemical reaction kinetics. This approach may play an important role in the future of systematic mechanochemical reaction discovery.
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