Demonstration of a Two‐Electron Pathway in Piezoelectric Mechanochemistry: Synthesis and Mechanical Adaptation of Polythiourethane

Mechanochemically initiated reactions have garnered interest as an unconventional method for generating new forms of reactivity. Previous studies have focused on radical‐mediated processes or two‐electron processes mediated by a ball‐milling mechanism. In this work, we present a novel mechano‐mediated reaction that utilizes focused ultrasound and mechanical vibration to generate both one‐electron and two‐electron thiol reactions in the same reaction pot. Interestingly, we find that the final reaction product can be biased depending on the reactive partner. We employ this newly reported two‐electron reaction to create the first vibrationally driven polythiourethane (PTU) through a two‐electron mechanism, as well as its adaptive polymer composites. This research presents an eco‐friendly, vibrationally promoted approach to polymer synthesis.