Force–Reactivity Property of a Single Monomer Is Sufficient To Predict the Micromechanical Behavior of Its Polymer

We demonstrate an accurate prediction of the micromechanical behavior of a single chain of cyclopropanated polybutadiene, which is governed by rapid isomerization of the cyclopropane moieties at 1.2 nN, from the force–rate correlation of this reaction measured in a small series of increasingly strained macrocycles. The data demonstrate that a single physical quantity, force, uniquely defines the dynamics across length scales from >100 to <1 nm and that strain imposed through molecular design and that imposed by micromanipulation techniques have equivalent effects on the kinetics of a chemical reaction. This represents a new method of screening potential monomers for applications in stress-responsive materials that could also facilitate atomistic interpretations of single-molecule force experiments.