Quantum interference plays an important role in charge transport through single-molecule junctions, even at room temperature. Of special interest is the measurement of the destructive quantum interference dip itself. Such measurements are especially demanding when performed in a continuous mode of operation. Here, we use mechanical modulation experiments at ambient conditions to reconstruct the destructive quantum interference dip of conductance versus displacement. Simultaneous measurements of the Seebeck coefficient show a sinusoidal response across the dip without sign change. Calculations that include electrode distance and energy alignment variations explain both observations quantitatively, emphasizing the crucial role of thermal fluctuations for measurements under ambient conditions. Our results open the way for establishing a closer link between break-junction experiments and theory in explaining single-molecule transport phenomena, especially when describing sharp features in the transmission.

The possibility to study quantum interference phenomena at ambient conditions is an appealing feature of molecular electronics. By connecting two porphyrins in a cofacial cyclophane, we create an attractive platform for mechanically controlling electric transport through the intramolecular extent of π-orbital overlap of the porphyrins facing each other and through the angle of xanthene bridges with regard to the porphyrin planes. We analyze theoretically the evolution of molecular configurations in the pulling process and the corresponding changes in electric conduction by combining density functional theory (DFT) with Landauer scattering theory of phase-coherent elastic transport. Predicted conductances during the stretching process show order of magnitude variations caused by two robust destructive quantum interference features that span through the whole electronic gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Mechanically-controlled break junction (MCBJ) experiments at room temperature verify the mechanosensitive response of the molecular junctions. During the continuous stretching of the molecule, they show conductance variations of up to 1.5 orders of magnitude over single breaking events. Uncommon triple-and quadruple-frequency responses are observed in periodic electrode modulation experiments with amplitudes of up to 10 Å. This further confirms the theoretically predicted double transmission dips caused by the spatial and energetic rearrangement of molecular orbitals, with contributions from both through-space and through-bond transport. This journal is

Quantum interference (QI) of electron waves passing through a single-molecule junction provides a powerful means to influence its electrical properties. Here, we investigate the correlation between substitution pattern, conductance, and mechanosensitivity in [2.2]paracyclophane (PCP)-based molecular wires in a mechanically controlled break junction experiment. The effect of the meta versus para connectivity in both the central PCP core and the phenyl ring connecting the terminal anchoring group is studied. We find that the meta-phenyl-anchored PCP yields such low conductance levels that molecular features cannot be resolved; in the case of para-phenyl-coupled anchoring, however, large variations in conductance values for modulations of the electrode separation occur for the pseudo-para-coupled PCP core, while this mechanosensitivity is absent for the pseudo-meta-PCP core. The experimental findings are interpreted in terms of QI effects between molecular frontier orbitals by theoretical calculations based on density functional theory and the Landauer formalism.

An appealing feature of molecular electronics is the possibility of inducing changes in the orbital structure through external stimuli. This can provide functionality on the single-molecule level that can be employed for sensing or switching purposes if the associated conductance changes are sizable upon application of the stimuli. Here, we show that the room-temperature conductance of a spring-like molecule can be mechanically controlled up to an order of magnitude by compressing or elongating it. Quantum-chemistry calculations indicate that the large conductance variations are the result of destructive quantum interference effects between the frontier orbitals that can be lifted by applying either compressive or tensile strain to the molecule. When periodically modulating the electrode separation, a conductance modulation at double the driving frequency is observed, providing a direct proof for the presence of quantum interference. Furthermore, oscillations in the conductance occur when the stress built up in the molecule is high enough to allow the anchoring groups to move along the surface in a stick-slip-like fashion. The mechanical control of quantum interference effects results in the largest-gauge factor reported for single-molecule devices up to now, which may open the door for applications in, e.g., a nanoscale mechanosensitive sensing device that is functional at room temperature.