Lewis-Acid Mediated Reactivity in Single-Molecule Junctions.

While chemical reactions at a gold electrode can be monitored using molecular conductance and driven by extrinsic stimuli, the intrinsic properties of the nanostructured interface may perform important additional functions that are not yet well understood. Here we evaluate these properties in studies of single-molecule junctions formed from components comprising 4,4'-biphenyl backbones functionalized with 12 different sulfur-based linker groups. With some linkers, we find evidence for S-C(sp) bond breaking, and C(sp)-C(sp) bond forming, reactions consistent with the transformations expected for those groups in the presence of a Lewis acid.