Prediction of the mechanochemical reactivity of triarylmethane-based mechanophores using the Constrained Geometries Simulate External Force method.

Abstract

In this study, a simple and accessible computational method, the constrained geometries simulate external force (CoGEF), was used to simulate the impact of mechanical stress on model mechanophores and predict their mechanochemical reactivity. The development of force-responsive molecules enables the design of polymers for applications such as damage reporting, stress sensing, and self-healing. Experimental development of mechanophores is often hindered due to a lack of understanding of structure-activity correlations. Simulation can assist in understanding such relationships and designing better mechanophores. A series of mechanophores was proposed and computationally studied using the CoGEF method at the B3LYP/6-31* level of theory, which applies an external tensile force to the molecule to predict mechanochemical bond rupture. This study provides insights into the roles of electron-withdrawing groups, linear hydrocarbon or ester groups, and solvents in the design of a new mechanophore before synthesis.