Examining the Impact of Relative Mechanophore Activity on the Selectivity of Ultrasound-Induced Mechanochemical Chain Scission.

Despite recent advances in polymer mechanochemistry, a more complete understanding of the factors that dictate the ultrasound-induced mechanochemical activation efficiency of mechanophores is necessary. Here, we examine how the identity of a mechanophore, and hence its unique force-coupled reactivity, affects the competition between mechanophore activation and nonspecific polymer backbone scission. Polymers incorporating distinct mechanophores but with putatively similar "chain-centeredness" exhibit widely different mechanochemical activation efficiencies. Furthermore, we employ mechanophores that can be orthogonally cleaved following ultrasonication using heat or light to report on the degree of nonspecific backbone scission that occurs for different mechanophore-containing polymers subjected to ultrasound-induced mechanical force. Our results illustrate that the identity of the mechanophore as well as its position in the polymer chain are inextricably important parameters that together control the selectivity of mechanophore activation during ultrasonication.