Michal Valášek

Single-Molecule Conductance in a Series of Extended Viologen Molecules.

Single-molecule conductance in a series of extended viologen molecules was measured at room temperature using a gold-molecule-gold scanning tunneling microscopy break junction arrangement. Conductance values for individual molecules change from 4.8 ± 1.2 nS for the shortest compound to 2.9 ± 1.0 nS for the compound with six repeating units and length of 11 nm. The latter value is almost 3 orders of magnitude higher than that reported for all-carbon-based aromatic molecular wires of comparable length. On the basis of the length of the molecules, an attenuation factor of only 0.06 ± 0.004 nm(-1) (0.006 ± 0.0004 Å(-1)) was obtained. To the best of our knowledge, this is the smallest value reported for the conductance attenuation in a series of molecular wires.

Measured and Calculated Oxidation Potentials of 1-X-12-Y-CB11Me10– Anions

Cyclic voltammetry of 31 icosahedral carborane anions 1-X-12-Y-CB(11)Me(10)(-) at a Pt electrode in liquid SO(2) revealed a completely reversible one-electron oxidation even at low scan rates, except for the anions with Y = I, which are oxidized irreversibly up to a scan rate of 5.0 V/s, and the anion with X = COOH and Y = H, whose oxidation is irreversible at scan rates below 1.0 V/s. Relative reversible oxidation potentials agree well with RI-B3LYP/TZVPP,COSMO and significantly less well with RI-BP86/TZVPP,COSMO or RI-HF/TZVPP,COSMO calculated adiabatic electron detachment energies. Correlations with HOMO energies of the anions are nearly as good, even though the oxidized forms are subject to considerable Jahn-Teller distortion. Except for the anion with X = F and Y = Me, the oxidation potentials vary linearly with substituent σ(p) Hammett constants. The slopes (reaction constants) are ~0.31 and ~0.55 V for positions 1 and 12, respectively.

Microwave-Assisted Alkylation of [CB11H12]- and Related Anions

A total of 19 permethylated derivatives of substituted [CB(11)H(12)](-) anions have been prepared using alkylation with microwave assistance. The reactions proceed much faster and more cleanly than under ordinary conditions. Microwave assistance is especially convenient for the permethylation of carborane anions carrying electron-withdrawing groups in positions 1 and/or 12. Even [1-F-CB(11)H(11)](-) can be undecamethylated, whereas under ordinary heating, it has only been hexamethylated.

First-principle-based MD description of azobenzene molecular rods

Extensive density functional theory (DFT) calculations have been performed to develop a force field for the classical molecular dynamics (MD) simulations of various azobenzene derivatives. Besides azobenzene, we focused on a thiolated azobenzene’s molecular rod (4′-{[(1,1′-biphenyl)-4-yl]diazenyl}-(1,1′-biphenyl)-4-thiol) that has been previously demonstrated to photoisomerize from trans to cis with high yields on surfaces. The developed force field is an extension of OPLS All Atoms, and key bonding parameters are parameterized to reproduce the potential energy profiles calculated by DFT. For each of the parameterized molecule, we propose three sets of parameters: one best suited for the trans configuration, one for the cis configuration, and finally, a set able to describe both at a satisfactory degree. The quality of the derived parameters is evaluated by comparing with structural and vibrational experimental data. The developed force field opens the way to the classical MD simulations of self-assembled monolayers (SAMs) of azobenzene’s molecular rods, as well as to the quantum mechanics/molecular mechanics study of photoisomerization in SAMs.

On the adsorption of extended viologens at the electrode|electrolyte interface.

Extended viologens represent a group of organic molecules intended to be used as molecular wires in molecular electronic devices. Adsorption properties of a novel series of extended viologen molecules were studied at the mercury electrode|electrolyte interface. These compounds form compact monolayers around the potential of zero charge with a constant differential capacitance value of 2.5 ± 0.2 μF cm(-2) independent of temperature, length of the molecule, and its bulk concentration. At more negative potentials their reduction in the adsorbed state takes place. We showed that the adsorption process is diffusion controlled and time needed to fully cover the electrode surface is independent of the electrode potential. A modified Koryta equation was employed for the calculation of the surface concentration of the adsorbates leading to the value of 5.3 × 10(-11) mol cm(-2) for the shortest wire and to 1.6 × 10(-11) mol cm(-2) for the longest one. Based on the space filling model and the differential capacitance value in the compact film region, it was postulated that these molecules lay flat on the electrode surface.

Rigid multipodal platforms for metal surfaces

Summary In this review the recent progress in molecular platforms that form rigid and well-defined contact to a metal surface are discussed. Most of the presented examples have at least three anchoring units in order to control the spatial arrangement of the protruding molecular subunit. Another interesting feature is the lateral orientation of these foot structures which, depending on the particular application, is equally important as the spatial arrangement of the molecules. The numerous approaches towards assembling and organizing functional molecules into specific architectures on metal substrates are reviewed here. Particular attention is paid to variations of both, the core structures and the anchoring groups. Furthermore, the analytical methods enabling the investigation of individual molecules as well as monomolecular layers of ordered platform structures are summarized. The presented multipodal platforms bearing several anchoring groups form considerably more stable molecule–metal contacts than corresponding monopodal analogues and exhibit an enlarged separation of the functional molecules due to the increased footprint, as well as restrict tilting of the functional termini with respect to the metal surface. These platforms are thus ideally suited to tune important properties of the molecule–metal interface. On a single-molecule level, several of these platforms enable the control over the arrangement of the protruding rod-type molecular structures (e.g., molecular wires, switches, rotors, sensors) with respect to the surface of the substrate.

An electrically actuated molecular toggle switch

Molecular electronics is considered a promising approach for future nanoelectronic devices. In order that molecular junctions can be used as electrical switches or even memory devices, they need to be actuated between two distinct conductance states in a controlled and reproducible manner by external stimuli. Here we present a tripodal platform with a cantilever arm and a nitrile group at its end that is lifted from the surface. The formation of a coordinative bond between the nitrile nitrogen and the gold tip of a scanning tunnelling microscope can be controlled by both electrical and mechanical means, and leads to a hysteretic switching of the conductance of the junction by more than two orders of magnitude. This toggle switch can be actuated with high reproducibility so that the forces involved in the mechanical deformation of the molecular cantilever can be determined precisely with scanning tunnelling microscopy.

Importance of the Anchor Group Position (Para versus Meta) in Tetraphenylmethane Tripods: Synthesis and Self‐Assembly Features

The efficient synthesis of tripodal platforms based on tetraphenylmethane with three acetyl-protected thiol groups in either meta or para positions relative to the central sp(3) carbon for deposition on Au (111) surfaces is reported. These platforms are intended to provide a vertical arrangement of the substituent in position 4 of the perpendicular phenyl ring and an electronic coupling to the gold substrate. The self-assembly features of both derivatives are analyzed on Au (111) surfaces by low-temperature ultra-high-vacuum STM, high-resolution X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and reductive voltammetric desorption studies. These experiments indicated that the meta derivative forms a well-ordered monolayer, with most of the anchoring groups bound to the surface, whereas the para derivative forms a multilayer film with physically adsorbed adlayers on the chemisorbed para monolayer. Single-molecule conductance values for both tripodal platforms are obtained through an STM break junction experiment.

Molecular Graph Paper

We present a self-assembled template that consists of tetraphenylmethane derivatives and adopts a periodic lateral arrangement on a Au(111) surface with acetyl groups sticking out of the molecular film. By using the tip of a scanning tunneling microscope, these acetyl groups can be removed in a spatially controlled way without significantly affecting the remaining molecular assembly. The chemically modified molecules can be readily distinguished from the original ones such that information can be engraved in the molecular film. Both the modified nature of an individual molecule and the order of the molecular film are shown to persist at room temperature. The mesh size of this molecular graph paper can be tuned by varying the length of the molecular spacer so that writing and reading information on the nanoscale with variable letter sizes becomes possible.

Spatial and Lateral Control of Functionality by Rigid Molecular Platforms

Surface mounted molecular devices have received significant attention in the scientific community because of their unique ability to construct functional materials. The key involves the platform on which the molecular device works on solid substrates, such as in solid-liquid or solid-vacuum interfaces. Here, we outline the concept of rigid molecular platforms to immobilize active functionality atop flat surfaces in a controllable manner. Most of these (multipodal) platforms have at least three anchoring groups to control the spatial arrangement of the protruding functional moieties and form mechanically stable and electronically tuned contacts to the underlying substrate. Another approach is based on employing of flat aromatic scaffolds bearing perpendicular functionalities that form stable lateral assemblies on various surfaces. Emphasis is placed on the need for controllable assembly and separation of these tailor-made molecules that expose functionalities at the molecular scale. The discussions are focused on the different molecular designs realizing functional 3D architectures on surfaces, the role of various anchoring strategies to control the spatial arrangement, and structural considerations controlling physical features like the coupling to the surface or the available space for sterically demanding molecular operations.