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

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Quantum interference (QI) within a single-molecule junction has become an essential yet powerful concept to integrate for designing molecular electronic devices.1 Recently we have investigated the correlation between substitution pattern, conductance and mechanosensitivity in [2.2]paracyclophane(PCP)-based single-molecule junction via the mechanically controlled break junction technique (MCBJ).2,3 We study the influence on conductance when we introduce meta/para connection to the PCP core and the phenyl ring attached to the anchoring group. We find that (i) meta-phenyl-anchored PCP yields such low conductance levels that molecular features cannot be resolved; (ii) para-phenyl-coupled anchoring generally gives higher conductance levels which can be detected via MCBJ; (iii) pseudo-para-coupled PCP core manifests large mechanosensitivity while (iv) pseudo-meta-coupled PCP core show the absence of mechanosensitivity. These 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.@en

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.

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