Force-Rate Characterization of Two Spiropyran-Based Molecular Force Probes

The mechanically accelerated ring-opening reaction of spiropyran to a colored merocyanine provides a useful method by which to image the molecular scale stress/strain distribution within a polymer, but the magnitude of the forces necessary for activation has yet to be quantified. Here, we report single molecule force spectroscopy studies of two spiropyran isomers. Ring opening on the time scale of tens of milliseconds is found to require forces of ∼240 pN, well below that of previously characterized covalent mechanophores. The lower threshold force is a combination of a low force-free activation energy and the fact that the change in rate with force (activation length) of each isomer is greater than that inferred in other systems. Finally, regiochemical effects on mechanochemical coupling are characterized, and increasing force reverses the relative ring opening rates of the two isomers.