Heterolytic Bond Cleavage in a Scissile Triarylmethane Mechanophore.

ABSTRACT

Covalent mechanophores display the cleavage of a weak covalent bond when a sufficiently high mechanical force is applied. Three different covalent bond breaking mechanisms have been documented thus far, including concerted, homolytic, and heterolytic scission. Motifs that display heterolytic cleavage typically separate according to non-scissile reaction pathways that afford zwitterions. Here, we report a new mechanochromic triarylmethane mechanophore, which dissociates according to a scissile heterolytic pathway and displays a pronounced mechanochromic response. The mechanophore was equipped with two styrenylic handles that allowed its incorporation as a cross-linker into poly(N,N-dimethylacrylamide) and poly(methyl acrylate-co-2-hydroxyethyl acrylate) networks. These materials are originally colorless, but compression or tensile deformation renders the materials colored. By combining tensile testing and in situ transmittance measurements, we show that this effect is related to scissile cleavage leading to colored triarylmethane carbocations.