Redox molecules with equilibrium potentials suitable for electrochemical control offer perspectives in nanoscale and single-molecule electronics. This applies to molecular wiring, but also towards higher sophistication such as transistor or diode function. Most recent nanoscale or single-molecule functional systems are, however, fraught with operational limitations such as cryogenic temperatures and ultra-high vacuum, or lack of electrochemical potential control. We report here cyclic voltammetry (CV) using single-crystal Au(111)- and Pt(111)-electrodes and electrochemical in situ scanning tunnelling microscopy (STM) of a class of Os(II)/(III)- and Co(II)/(III)-complexes, the former novel in molecular electronics. The complexes are robust, with ligand groups suitable for linking the complexes to the Au(111)- and Pt(111)-surfaces via N- and S-donor atoms. The CV data reflect monolayer behaviour. Interfacial ET of the Os-complexes is fast, k0ET
≥ 106 s−1, while the Co-complex reacts much more slowly, k0ET
× 103 s−1. In situ STM of the Os-complexes shows a maximum in the tunnelling current/overpotential relation at constant bias voltage with up to 50-fold current rise. The peak position follows systematically the bias voltage and equilibrium potential, in keeping with theoretical frames for two-step electron transfer (ET) of in situ STM of redox molecules. The molecular conductivity behaves broadly similarly. The Co-complex also shows a tunnelling spectroscopic feature but much weaker than the Os-complexes. This can be ascribed to the much smaller interfacial ET rate constant, again caused by large intramolecular nuclear reorganization and weak electronic coupling to the substrate electrode. Overall the study has mapped the properties of target molecules needed for stable electronic switching, of possible importance in molecular electronics towards the single-molecule level, in room temperature condensed matter environment.
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