Single-molecule contact switching <i>via</i> electro-inductive effects

The non-faradaic application of electric fields generated at the surface of charged electrodes to polarize bound molecules, also termed as electro-inductive effects, have recently attracted increasing attention in modifying the chemical reactivity of molecules in electrosynthesis. Herein, we applied this electro-inductive effect to control the Lewis adduct formation and dissociation between BF₃ and pyridine N of heterocycles to realize single-molecule contact switching. <i>In situ</i> single-molecule conductance measurements, <i>in situ</i> Raman analysis and theoretical calculations clearly show that the outward electric field along the positively-charged electrode surface polarizes adsorbed molecules to withdraw electron density from the terminal pyridine N, which weakens the N-BF₃ Lewis bond for dissociation upon applied positive potentials. The released unbounded pyridine N can connect the molecule into a molecular circuit for electron transfer (considered as the "ON" state). Meanwhile, the inward electric field along the negatively charged electrode surface promotes the formation of an N-BF₃ Lewis bond, leading to breaking of the molecular circuit (considered as the "OFF" state). Combined with the optimization of BF₃ concentration from the equilibrium BF₄ ^- ⇌ BF₃ + F^-, the electro-inductive effect can reversibly switch single-molecule conductance in conductance measurements and tunnelling currents in <i>I</i>-<i>V</i> measurements.