Impact of a Mechanical Bond on the Activation of a Mechanophore

Mechanical bonds are known to efficiently absorb mechanical energy at low forces, but their behavior at high forces is unknown. Here we investigate the impact of a mechanical bond on the rate of activation of a Diels–Alder mechanophore. Using a combination of experimental and computational techniques, we found that the rate of a retro-Diels–Alder reaction under tension is decreased when the mechanophore is embedded in the axle of a rotaxane due to the presence of a competing high-stress region at the junction between the macrocycle and the axle.