The Impact of <i>E</i>−<i>Z</i> Photo-Isomerization on Single Molecular Conductance

The single molecule conductance of the E and Z isomers of 4,4′-(ethene-1,2-diyl)dibenzoic acid has been determined using two scanning tunneling microscopy (STM) methods for forming molecular break junctions [the I(s) (I = current and s is distance) method and the in situ break junction technique]. Isomerization leads to significant changes in the electrical conductance of these molecules, with the Z isomer exhibiting a higher conductance than the E isomer. Isomerization is achieved directly on the gold surface through photoirradiation, and the STM is used to determine conductance before and after irradiation; reversible switching between the two isomers could be achieved through irradiation of the surface bound species at different wavelengths. In addition, three groups of molecular conductance values [A (“low”), B (“medium”), and C (“high”)] have been measured for these carboxylate-terminated molecules. The origin of these conductance groups as well as the increase of the conductance for the Z isomer have been analyzed by comparing the length of the molecules extended in the gap, derived from molecular modeling, with the experimentally observed break-off distance for both isomers

Determination of Size and Concentration of Gold Nanoparticles from UV−Vis Spectra

The dependence of the optical properties of spherical gold nanoparticles on particle size and wavelength were analyzed theoretically using multipole scattering theory, where the complex refractive index of gold was corrected for the effect of a reduced mean free path of the conduction electrons in small particles. To compare these theoretical results to experimental data, gold nanoparticles in the size range of 5 to 100 nm were synthesized and characterized with TEM and UV−vis. Excellent agreement was found between theory and experiment. It is shown that the data produced here can be used to determine both size and concentration of gold nanoparticles directly from UV−vis spectra. Equations for this purpose are derived, and the precision of various methods is discussed. The major aim of this work is to provide a simple and fast method to determine size and concentration of nanoparticles

Influence of Conformational Flexibility on Single-Molecule Conductance in Nano-Electrical Junctions

The temperature dependence of the single-molecule conductance of conformationally flexible alkanedithiol molecular bridges is compared to that of more rigid analogues which contain cyclohexane ring(s). Molecular conductance has been measured with a scanning tunneling microscope (STM) at fixed gap separation by observing the stochastic formation of molecule bridges between a gold STM tip and substrate (the so-called “I(t)” technique). Under these conditions, the junction can be populated by a wide distribution of conformers of alkanedithiol molecular bridges and a strong temperature dependence of the single-molecule conductance is observed. By contrast the rigid analogues that contain cyclohexane ring(s), which cannot form the thermally accessible gauche rich conformers open to the alkanedithiols, show no dependence of the single-molecule conductance on temperature. This comparison demonstrates that it is the conformational flexibility and access to thermally populated higher energy conformers of the linear polymethylene (alkane) bridges which leads to the temperature dependence. By removing this possibility in the cyclohexane ring-containing bridges, this conformational gating is excluded and the temperature dependence is then effectively suppressed

Impact of Junction Formation Method and Surface Roughness on Single Molecule Conductance

In recent years, several experimental studies have shown that different values of single molecule conductance can be observed for the same type of molecule. Although this observation has been tentatively attributed either to differing molecular conformations or to differing contact geometries, the reason for the different conductance groups remains still unclear. To elucidate this issue, a comparison of four different experimental methods to measure single molecule conductance is presented here for the case of alkanedithiols between gold electrodes, which is considered to be a model system. Three different fundamental conductance groups exhibiting low, medium, and high conductance, respectively, were observed for each molecule. The comparison of measurements performed on surface areas with different step densities reveals that the medium (high) conductance group can be attributed to the adsorption of one (two) contacting S atoms at step sites, whereas the low conductance group can be attributed to molecules adsorbed between flat surface regions. This finding is corroborated by a gap separation analysis for the different conduction groups, by matrix isolation measurements, and by a comparison of the results presented here with conductance measurements performed on self-assembled monolayers. The results presented here help to resolve apparent discrepancies in single molecule conductance measurements and are of general significance for molecular electronics and electrochemistry, since they show how molecular conductance is influenced by the contact morphology and, thus, by the atomic structure of the substrate surface

Redox State Dependence of Single Molecule Conductivity

Spontaneous formation of stable molecular wires between a gold scanning tunneling microscopy (STM) tip and substrate is observed when the sample has a low coverage of α,ω-dithiol molecules and the tunneling resistance is made sufficiently small. Current−distance curves taken under these conditions exhibit characteristic current plateaux at large tip−substrate separations from which the conductivity of a single molecule can be obtained. The versatility of this technique is demonstrated using redox-active molecules under potential control, where substantial reversible conductivity changes from 0.5 to 2.8 nS were observed when the molecule was electrochemically switched from the oxidized to the reduced state

Structure−Property Relationships in Redox-Gated Single Molecule Junctions − A Comparison of Pyrrolo-Tetrathiafulvalene and Viologen Redox Groups

Structure−Property Relationships in Redox-Gated Single Molecule Junctions − A Comparison of Pyrrolo-Tetrathiafulvalene and Viologen Redox Group

Single Molecule Conductance of Porphyrin Wires with Ultralow Attenuation

Single Molecule Conductance of Porphyrin Wires with Ultralow Attenuatio