Exploring relationships between chemical structure and molecular conductance: from α,ω-functionalised oligoynes to molecular circuits

The quantum circuit rule (QCR) allows estimation of the conductance of molecular junctions, electrode vertical bar X-bridge-Y vertical bar electrode, by considering the molecule as a series of independent scattering regions associated with the anchor groups (X, Y) and bridge, provided the numerical parameters that characterise the anchor groups (a(X), a(Y)) and molecular backbones (b(B)) are known. Single-molecule conductance measurements made with a series of alpha,omega-substituted oligoynes (X-{(C C)(N)}-X, N = 1, 2, 3, 4), functionalised by terminal groups, X (4-thioanisole (C6H4SMe), 5-(3,3-dimethyl-2,3-dihydrobenzo[b]thiophene) (DMBT), 4-aniline (C6H4NH2), 4-pyridine (Py), capable of serving as 'anchor groups' to contact the oligoyne fragment within a molecular junction, have shown the expected exponential dependence of molecular conductance, G, with the number of alkyne repeating units. In turn, this allows estimation of the anchor (a(i)) and backbone (b(i)) parameters. Using these values, together with previously determined parameters for other molecular fragments, the QCR is found to accurately estimate the junction conductance of more complex molecular circuits formed from smaller components assembled in series.

Automated summary

The quantum circuit rule (QCR) estimates the conductance of molecular junctions by considering them as a series of independent scattering regions associated with anchor groups and bridge. Single-molecule conductance measurements with substituted oligoynes demonstrate an exponential dependence of molecular conductance on the number of alkyne repeating units, allowing estimation of anchor and backbone parameters. The QCR accurately estimates the junction conductance of more complex molecular circuits formed from smaller components assembled in series, by utilizing these parameters in addition to previously determined ones.