Pushing vs Pulling: The Unique Geometry of Mechanophore Activation in a Rotaxane Force Actuator.

Mechanophores (mechanosensitive molecules) are usually activated by pulling them with covalently attached polymers. A rotaxane actuator offers a new geometry of activation as the macrocycle pushes against a stoppering mechanophore. Here we compare both pulling and pushing activations and show that pushing is more efficient and selective than pulling. We found that the pulling activation of a bulky furan/maleimide adduct occurs via two competing dissociation pathways: retrocycloaddition and heterolytic cleavage (generating a trityl cation in the process), while the same adduct only cleaves by retrocycloaddition during pushing activation. These results further demonstrate the efficacy and versatility of rotaxane actuators.