Enhancing Mechanochemical Activation in the Bulk State by Designing Polymer Architectures.

Mechanoresponsive polymers can have attractive functions; however, the relationship between polymer architecture and mechanoresponsiveness in the bulk state is still poorly understood. Here, we designed well-defined linear and star polymers with a mechanophore at the center of each architecture, and investigated the effect of molecular weight and branched structures on mechanoresponsiveness in the solid state. Diarylbibenzofuranone, which can undergo homolytic cleavage of the central C-C bond by mechanical force to form blue-colored radicals, was used as a mechanophore because the cleaved radicals could be evaluated quantitatively using electron paramagnetic resonance measurements. We confirmed that longer polymer chains induce mechanochemical activation more effectively and found that, in the bulk state, the star polymers have higher sensitivity to mechanical stress compared with a linear polymer having similar molecular weight arm segment.