A key target in molecular electronics has been molecules having switchable electrical properties. Switching between two electrical states has been demonstrated using such stimuli as light, electrochemical voltage, complexation and mechanical modulation. A classic example of the latter is the switching of 4,4'-bipyridine, leading to conductance modulation of around 1 order of magnitude. Here, we describe the use of side-group chemistry to control the properties of a single-molecule electromechanical switch, which can be cycled between two conductance states by repeated compression and elongation. While bulky alkyl substituents inhibit the switching behavior, π-conjugated side-groups reinstate it. DFT calculations show that weak interactions between aryl moieties and the metallic electrodes are responsible for the observed phenomenon. This represents a significant expansion of the single-molecule electronics "tool-box" for the design of junctions with electromechanical properties.

A key area of activity in contemporary molecular electronics is the chemical control of conductance of molecular junctions and devices. Here we study and modify a range of pyrrolodipyridines (carbazole-like) molecular wires. We are able to change the electrical conductance and quantum interference patterns by chemically regulating the bridging nitrogen atom in the tricyclic ring system. A series of eight different N-substituted pyrrolodipyridines has been synthesized and subjected to single-molecule electrical characterization using an STM break junction. Correlations of these experimental data with theoretical calculations underline the importance of the pyrrolic nitrogen in facilitating conductance across the molecular bridge and controlling quantum interference. The large chemical modulation for the meta-connected series is not apparent for the para-series, showing the competition between (i) meta-connectivity quantum interference phenomena and (ii) the ability of the pyrrolic nitrogen to facilitate conductance, that can be modulated by chemical substitution.

When two adjacent molecules are slid across each other, quantum interference causes oscillations in their conductance and Seebeck coefficient.