Nuclear Magnetic Resonance Chemical Shift as a Probe for Single-Molecule Charge Transport

Existing modelling tools, developed to aid the design of efficient molecular wires and to better understand their charge-transport behaviour and mechanism, have limitations in accuracy and computational cost. Further research is required to develop faster and more precise methods that can yield information on how charge transport properties are impacted by changes in the chemical structure of a molecular wire. In this study, we report a clear semilogarithmic correlation between charge transport efficiency and nuclear magnetic resonance chemical shifts in multiple series of molecular wires, also accounting for the presence of chemical substituents. The NMR data was used to inform a simple tight-binding model that accurately captures the experimental single-molecule conductance values, especially useful in this case as more sophisticated density functional theory calculations fail due to inherent limitations. Our study demonstrates the potential of NMR spectroscopy as a valuable tool for characterising, rationalising, and gaining additional insights on the charge transport properties of single-molecule junctions. The chemical shift observed in NMR spectroscopy has been recently found to be a descriptor for the frontier molecular orbitals of organic/organometallic compounds. In this manuscript, we demonstrate that it can be applied to rationalise charge transport through such compounds, equipping the molecular electronics toolbox with another useful technique.+ image