Elizabeth Tran

Redox Site-Mediated Charge Transport in a Hg−SAM//Ru(NH3)63+/2+//SAM−Hg Junction with a Dynamic Interelectrode Separation: Compatibility with Redox Cycling and Electron Hopping Mechanisms

This paper describes the formation and electrical properties of a new Hg-based metal-molecules-metal junction that incorporates charged redox sites into the space between the electrodes. The junction is formed by bringing into contact two mercury-drop electrodes whose surfaces are covered by COO(-)-terminated self-assembled monolayers (SAMs) and immersed in a basic aqueous solution of Ru(NH(3))(6)Cl(3). The electrical behavior of the junction, which is contacted at its edges by aqueous electrolyte solution, has been characterized electrochemically. This characterization shows that current flowing through the junction on the initial potential cycles is dominated by a redox-cycling mechanism and that the rates of electron transport can be controlled by controlling the potentials of the mercury electrodes with respect to the redox potential of the Ru(NH(3))(6)(3+/2+) couple. On repeated cycling of the potential across the junction, the current across it increases by as much as a factor of 40, and this increase is accompanied by a large (>300 mV) negative shift in the formal potential for the reduction of Ru(NH(3))(6)(3+). The most plausible rationalization of this behavior postulates a decrease in the size of the gap between the electrodes with cycling and a mechanism of conduction dominated by physical diffusion of Ru(NH(3))(6)(3+/2+) ions (at larger interelectrode spacing), with a possible contribution of electron hopping to charge transport (at smaller interelectrode spacing). In this rationalization, the negative shift in the formal potential plausibly reflects extrusion of the solution of electrolyte from the junction and an increase in the effective concentration of negatively charged species (surface-immobilized COO(-) groups) in the volume bounded by the electrodes. This junction has the characteristics required for use in screening and in exploratory work, involving nanogap electrochemical systems, and in mechanistic studies involving these systems. It does not have the stability needed for long-term technological applications.

Gating current flowing through molecules in metal–molecules–metal junctions

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.

Electron exchange between two electrodes mediated by two electroactive adsorbates.

Experimental data for electron exchange between two electrodes covered by electroactive films are presented and discussed in terms of the Gerischer model. A model Hamiltonian is proposed for such indirect electron exchange involving two intermediate species. Explicit model calculations are performed for the case in which the coupling between the two adsorbates is weak and determines the overall rate. The calculations agree well with the experimental data, and can be used to determine the energy of reorganization associated with the electron transfer.