Andrea Vezzoli

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.

Single-Molecule Conductance of Viologen–Cucurbit[8]uril Host–Guest Complexes

The local molecular environment is a critical factor which should be taken into account when measuring single-molecule electrical properties in condensed media or in the design of future molecular electronic or single molecule sensing devices. Supramolecular interactions can be used to control the local environment in molecular assemblies and have been used to create microenvironments, for instance, for chemical reactions. Here, we use supramolecular interactions to create microenvironments which influence the electrical conductance of single molecule wires. Cucurbit[8]uril (CB[8]) with a large hydrophobic cavity was used to host the viologen (bipyridinium) molecular wires forming a 1:1 supramolecular complex. Significant increases in the viologen wire single molecule conductances are observed when it is threaded into CB[8] due to large changes of the molecular microenvironment. The results were interpreted within the framework of a Marcus-type model for electron transfer as arising from a reduction in outer-sphere reorganization energy when the viologen is confined within the hydrophobic CB[8] cavity.

Resonant transport and electrostatic effects in single-molecule electrical junctions

This research was supported by the EPSRC (Grant No. EP/H035184/1), by MINECO under Grant No. FIS2013-47328, by the European Union structural funds and the Comunidad de Madrid MAD2D-CM Program under Grant. P2013/MIT-2850, and by Generalitat Valenciana under Grant PROMETEO/2012/011.

Low variability of single-molecule conductance assisted by bulky metal–molecule contacts

A detailed study of the trimethylsilylethynyl moiety, –CCSiMe3 (TMSE), as an anchoring group in metal|molecule|metal junctions, using a combination of experiment and density functional theory is presented. It is shown that the TMSE anchoring group provides improved control over the molecule–substrate arrangement within metal|molecule|metal junctions, with the steric bulk of the methyl groups limiting the number of highly transmissive binding sites at the electrode surface, resulting in a single sharp peak in the conductance histograms recorded by both the in situ break junction and I(s) STM techniques. As a consequence of the low accessibility of the TMSE group to surface binding configurations of measurable conductance, only about 10% of gold break junction formation cycles result in the clear formation of molecular junctions in the experimental histograms. The DFT-computed transmission characteristics of junctions formed from the TMSE-contacted oligo(phenylene)ethynylene (OPE)-based molecules described here are dominated by tunneling effects through the highest-occupied molecular orbitals (HOMOs). This gives rise to similar conductance characteristics in these TMSE-contacted systems as found in low conductance-type junctions based on comparably structured OPE-derivatives with amine-contacts that also conduct through HOMO-based channels.

Unconventional Single-Molecule Conductance Behavior for a New Heterocyclic Anchoring Group: Pyrazolyl

Electrical conductance across a molecular junction is strongly determined by the anchoring group of the molecule. Here we highlight the unusual behavior of 1,4-bis(1H-pyrazol-4-ylethynyl)benzene that exhibits unconventional junction current versus junction-stretching distance curves, which are peak-shaped and feature two conducting states of 2.3 × 10-4 G0 and 3.4 × 10-4 G0. A combination of theory and experiments is used to understand the conductance of single-molecule junctions featuring this new anchoring group, i.e., pyrazolyl. These results demonstrate that the pyrazolyl moiety changes its protonation state and contact binding during junction evolution and that it also binds in either end-on or facial geometries with gold contacts. The pyrazolyl moiety holds general interest as a contacting group, because this linkage leads to a strong double anchoring of the molecule to the gold electrode, resulting in enhanced conductance values.

Klaus Wandelt (Ed): Surface and Interface Science. Volume 5: Solid–Gas Interfaces I/Volume 6: Solid–Gas Interfaces II

metal oxides), and non-linear phenomena occurring at surfaces. A full chapter is devoted to statistical surface thermodynamics, and the volume ends with a review of the present advances in scanning probe manipulation of adsorbates on conductive surfaces. The overall presentation is very clear, and the reader is efficiently guided through the vast amount of material presented, making the 1500 pages composing the two volumes relatively easy to follow and digest. I found particularly interesting and well-presented the discussion of gas adsorption on semiconducting and metal oxide surfaces, where the authors make an extremely good job at reviewing such complex systems and the chemical processes occurring at their interfaces. The last chapter, describing the manipulation of atoms and molecule with a scanning tunnelling microscope, is the only one that, in my opinion, would benefit from a more thorough discussion on the chemistry and the chemical reactions happening at the surface. A few paragraphs on the recent advances in tip-assisted chemistry and electrochemistry in the scanning probe environment would have greatly expanded the focus of the chapter, ensuring a more comprehensive discussion. These volumes are clearly not designed as an introduction to the field, and a degree of knowledge of surface science is needed to follow the discussion. To the experienced scientist they represent a useful collection of important concepts supported by a vast bibliography, and I am sure that I will find myself consulting these books more than a few times over the next few years. Bibliography Surface and Interface Science.

Liverpool dataset from 'Gating of single molecule junction conductance by charge transfer complex formation'; A. Vezzoli et al., Nanoscale; DOI: 10.1039/c5nr04420k

The solid-state structures of organic charge transfer (CT) salts are critical in determining their mode of charge transport, and hence their unusual electrical properties, which range from semiconducting through metallic to superconducting. In contrast, using both theory and experiment, we show here that the conductance of metal |single molecule| metal junctions involving aromatic donor moieties (dialkylterthiophene, dialkylbenzene) increase by over an order of magnitude upon formation of charge transfer (CT) complexes with tetracyanoethylene (TCNE). This enhancement occurs because CT complex formation creates a new resonance in the transmission function, close to the metal contact Fermi energy, that is a signal of room-temperature quantum interference.