Marcel Mayor

Driving current through single organic molecules.

We investigate electronic transport through two types of conjugated molecules. Mechanically controlled break junctions are used to couple thiol end groups of single molecules to two gold electrodes. Current-voltage characteristics ( IVs) of the metal-molecule-metal system are observed. These IVs reproduce the spatial symmetry of the molecules with respect to the direction of current flow. We hereby unambiguously detect an intrinsic property of the molecule and are able to distinguish the influence of both the molecule and the contact to the metal electrodes on the transport properties of the compound system.

Experimental evidence for the functional relevance of anion– π interactions

Attractive in theory and confirmed to exist, anion-pi interactions have never really been seen at work. To catch them in action, we prepared a collection of monomeric, cyclic and rod-shaped naphthalenediimide transporters. Their ability to exert anion-pi interactions was demonstrated by electrospray tandem mass spectrometry in combination with theoretical calculations. To relate this structural evidence to transport activity in bilayer membranes, affinity and selectivity sequences were recorded. pi-acidification and active-site decrowding increased binding, transport and chloride > bromide > iodide selectivity, and supramolecular organization inverted acetate > nitrate to nitrate > acetate selectivity. We conclude that anion-pi interactions on monomeric surfaces are ideal for chloride recognition, whereas their supramolecular enhancement by pi,pi-interactions appears perfect to target nitrate. Chloride transporters are relevant to treat channelopathies, and nitrate sensors to monitor cellular signaling and cardiovascular diseases. A big impact on organocatalysis can be expected from the stabilization of anionic transition states on chiral pi-acidic surfaces.

Light‐Powered Electrical Switch Based on Cargo‐Lifting Azobenzene Monolayers

Inspired by the complex molecular machines found in nature, chemists have developed much simpler molecular motors. Among them, several systems incorporating azobenzene have been proposed, which exploit the reversible trans–cis isomerization triggered by light or an electric field for applications such as optical data-storage devices, switchable supramolecular cavities, and sensors. Recently, it has been demonstrated that the photoisomerization process of individual polymer chains incorporating azobenzenes can express mechanical work. In light of these findings, one can foresee self-assembled monolayers (SAMs) of aromatic azobenzenes as molecular systems able to express forces of unprecedented magnitude by exploiting a collective subnanometer structural change. We recently designed a rigid and fully conjugated azobenzene exposing a thiol anchoring group, which was able to form a tightly packed SAM on Au(111) (SAMAZO). Scanning tunneling microscopy (STM) studies revealed that upon light irradiation of the chemisorbed SAMs, a collective isomerization of entire molecular-crystalline domains occurred with an outstandingly high directionality. Based on these results, a cooperative nature of the isomerization of adjacent AZO molecules has been proposed. Furthermore, the joint action of the molecules in the SAM provides an ideal system as a potential “cargo” lifter. Herein, we show that, upon irradiation, azobenzene SAMs incorporated in a junction between an Au(111) surface and a mercury drop are able to 1) lift the “heavy” Hg drop, and 2) reversibly photoswitch the current flowing through the junction (Figure 1). Current–voltage (I–V) characteristics averaged over more than 30 junctions incorporating AZO SAMs in the trans and the cis conformations are shown in Figure 2a. The SAMAZO in the cis conformation was obtained with extremely high yield (98%) upon irradiation by UV light of the SAMAZO initially formed by the trans conformer. The difference in the measured currents, which amounts to about 1.4 orders of magnitude, is in agreement with a through-bond tunneling mechanism described by Equation (1).

Molecular junctions based on aromatic coupling

If individual molecules are to be used as building blocks for electronic devices, it will be essential to understand charge transport at the level of single molecules. Most existing experiments rely on the synthesis of functional rod-like molecules with chemical linker groups at both ends to provide strong, covalent anchoring to the source and drain contacts. This approach has proved very successful, providing quantitative measures of single-molecule conductance, and demonstrating rectification and switching at the single-molecule level. However, the influence of intermolecular interactions on the formation and operation of molecular junctions has been overlooked. Here we report the use of oligo-phenylene ethynylene molecules as a model system, and establish that molecular junctions can still form when one of the chemical linker groups is displaced or even fully removed. Our results demonstrate that aromatic pi-pi coupling between adjacent molecules is efficient enough to allow for the controlled formation of molecular bridges between nearby electrodes.

Cooperative light-induced molecular movements of highly ordered azobenzene self-assembled monolayers

Photochromic systems can convert light energy into mechanical energy, thus they can be used as building blocks for the fabrication of prototypes of molecular devices that are based on the photomechanical effect. Hitherto a controlled photochromic switch on surfaces has been achieved either on isolated chromophores or within assemblies of randomly arranged molecules. Here we show by scanning tunneling microscopy imaging the photochemical switching of a new terminally thiolated azobiphenyl rigid rod molecule. Interestingly, the switching of entire molecular 2D crystalline domains is observed, which is ruled by the interactions between nearest neighbors. This observation of azobenzene-based systems displaying collective switching might be of interest for applications in high-density data storage.

Azobenzenes as Light-Controlled Molecular Electronic Switches in Nanoscale Metal−Molecule−Metal Junctions

Conductance switching associated with the photoisomerization of azobenzene-based (Azo) molecules was observed in nanoscopic metal-molecule-metal junctions. The junctions were formed by using a conducting atomic force microscope (C-AFM) approach, where a metallic AFM tip was used to electrically contact a gold-supported Azo self-assembled monolayer. The measured 30-fold increase in conductance is consistent with the expected decrease in tunneling barrier length resulting from the conformational change of the Azo molecule.

Quantum interference of large organic molecules

The wave nature of matter is a key ingredient of quantum physics and yet it defies our classical intuition. First proposed by Louis de Broglie a century ago, it has since been confirmed with a variety of particles from electrons up to molecules. Here we demonstrate new high-contrast quantum experiments with large and massive tailor-made organic molecules in a near-field interferometer. Our experiments prove the quantum wave nature and delocalization of compounds composed of up to 430 atoms, with a maximal size of up to 60 Å, masses up to m=6,910 AMU and de Broglie wavelengths down to λdB=h/mv≃1 pm. We show that even complex systems, with more than 1,000 internal degrees of freedom, can be prepared in quantum states that are sufficiently well isolated from their environment to avoid decoherence and to show almost perfect coherence.

Single-molecule junctions based on nitrile-terminated biphenyls : a promising new anchoring group

We present a combined experimental and theoretical study of the electronic transport through single-molecule junctions based on nitrile-terminated biphenyl derivatives. Using a scanning tunneling microscope-based break-junction technique, we show that the nitrile-terminated compounds give rise to well-defined peaks in the conductance histograms resulting from the high selectivity of the N-Au binding. Ab initio calculations have revealed that the transport takes place through the tail of the LUMO. Furthermore, we have found both theoretically and experimentally that the conductance of the molecular junctions is roughly proportional to the square of the cosine of the torsion angle between the two benzene rings of the biphenyl core, which demonstrates the robustness of this structure-conductance relationship.

Electronic transport through single conjugated molecules

Abstract We investigate electronic transport through single conjugated molecules, and compare our data to results of quantum chemical calculations. Conductance spectra of two types of molecules are studied in a metal–molecule–metal junction established using the mechanically controlled break-junction technique. We observe a suppressed conductance at low bias, characteristic step-like features at higher voltages, and strong sample-to-sample fluctuations. We develop a quantum-chemical model for our system using DFT calculations, with the electrodes modelled by small clusters. We consider the effects of different geometries of molecule–metal configurations and bonding as well as finite electric field, and are thereby able to account for the phenomenology of the experimental data.

Electrical conductance of conjugated oligomers at the single molecule level.

We determine and compare, at the single molecule level and under identical environmental conditions, the electrical conductance of four conjugated phenylene oligomers comprising terminal sulfur anchor groups with simple structural and conjugation variations. The comparison shows that the conductance of oligo(phenylene vinylene) (OPV) is slightly higher than that of oligo(phenylene ethynylene) (OPE). We find that solubilizing side groups do neither prevent the molecules from being anchored within a break junction nor noticeably influence the conductance value.