Gating current flowing through molecules in

We have assembled two junctions that incorporate redox sites between Hg electrodes by different interactions. In the first junction, Hg-SAM-R//R-SAM–Hg, the redox site (R) are covalently linked to each electrode in self assembled monolayers (SAM-R). In the second junction, Hg–SAM//R//SAM–Hg, the redox sites dissolved in solution are trapped by electrostatic interaction at the SAM formed at the electrodes. The current flowing through these junctions can be controlled by adjusting the potential applied at the electrodes with respect to the redox potential of the species by using an electrochemical system. The current flowing in these two junctions is mediated by the redox sites through different mechanisms. In particular, the current flowing through the Hg–SAM-R//R-SAM–Hg junction occurs through a self exchange mechanism between the redox sites organized at each electrode, while the current flowing through the Hg–SAM//R//SAM–Hg junction is dominated by a redox-cycling mechanism. The systems described here are easy to assemble, well-characterized, yield reproducible data and make it easy to modify the electrical properties of the junctions by changing the nature of the redox centres. For these characteristics they are well suited for collecting fundamental information relevant to the fabrication of molecular switches. 1