Single-Molecule Conductance Studies of Organometallic Complexes Bearing 3-Thienyl Contacting Groups.

The compounds and complexes 1,4-C6 H4 (C≡C-cyclo-3-C4 H3 S)2 (2), trans-[Pt(C≡C-cyclo-3-C4 H3 S)2 (PEt3 )2 ] (3), trans-[Ru(C≡C-cyclo-3-C4 H3 S)2 (dppe)2 ] (4; dppe=1,2-bis(diphenylphosphino)ethane) and trans-[Ru(C≡C-cyclo-3-C4 H3 S)2 {P(OEt)3 }4 ] (5) featuring the 3-thienyl moiety as a surface contacting group for gold electrodes have been prepared, crystallographically characterised in the case of 3-5 and studied in metal|molecule|metal junctions by using both scanning tunnelling microscope break-junction (STM-BJ) and STM-I(s) methods (measuring the tunnelling current (I) as a function of distance (s)). The compounds exhibit similar conductance profiles, with a low conductance feature being more readily identified by STM-I(s) methods, and a higher feature by the STM-BJ method. The lower conductance feature was further characterised by analysis using an unsupervised, automated multi-parameter vector classification (MPVC) of the conductance traces. The combination of similarly structured HOMOs and non-resonant tunnelling mechanism accounts for the remarkably similar conductance values across the chemically distinct members of the family 2-5.

Electrochemical Single-Molecule Transistors with Optimized Gate Coupling.

Electrochemical gating at the single molecule level of viologen molecular bridges in ionic liquids is examined. Contrary to previous data recorded in aqueous electrolytes, a clear and sharp peak in the single molecule conductance versus electrochemical potential data is obtained in ionic liquids. These data are rationalized in terms of a two-step electrochemical model for charge transport across the redox bridge. In this model the gate coupling in the ionic liquid is found to be fully effective with a modeled gate coupling parameter, ξ, of unity. This compares to a much lower gate coupling parameter of 0.2 for the equivalent aqueous gating system. This study shows that ionic liquids are far more effective media for gating the conductance of single molecules than either solid-state three-terminal platforms created using nanolithography, or aqueous media.

Simplifying the conductance profiles of molecular junctions: the use of the trimethylsilylethynyl moiety as a molecule-gold contact.

Conductance across a metal|molecule|metal junction is strongly influenced by the molecule-substrate contacts, and for a given molecular structure, multiple conductance values are frequently observed and ascribed to distinct binding modes of the contact at each of the molecular termini. Conjugated molecules containing a trimethylsilylethynyl terminus, -C≡CSiMe(3) give exclusively a single conductance value in I(s) measurements on gold substrates, the value of which is similar to that observed for the same molecular backbone with thiol and amine based contacting groups when bound to under-coordinated surface sites.