Is Molecular Weight or Degree of Polymerization a Better Descriptor of Ultrasound-Induced Mechanochemical Transduction?

A detailed understanding of the fundamental processes that govern mechanical transduction in covalent polymer mechanochemistry is essential to advance innovation in this field. In contrast to progress in the development of new mechanophores, the influence of polymer structure and composition on mechanochemical activity has received relatively little attention. In order to address this gap in knowledge, a continuous flow system with synchronous UV-vis absorption capabilities was designed to quantify the ultrasound-induced mechanical activation of a spiropyran mechanophore in real-time. Measurements of reaction kinetics with polymer tethers of varying repeating unit structure demonstrate that degree of polymerization is the key descriptor of mechanochemical activity, independent of molecular weight and pendant group constitution. These results have important implications for the rationalization of mechanochemical properties and the design of new mechanochemically active polymer systems.