RESUMEN
Integration of molecular switching units into complex electronic circuits is considered to be the next step toward the realization of novel logic and memory devices. This paper reports on an ordered 2D network of neighboring ternary switching units represented by triazatruxene (TAT) molecules organized in a honeycomb lattice on a Ag(111) surface. Using low-temperature scanning tunneling microscopy, the bonding configurations of individual TAT molecules can be controlled, realizing up to 12 distinct states per molecule. The switching between those states shows a strong bias dependence ranging from tens of millivolts to volts. The low-bias switching behavior is explored in active units consisting of two and more interacting TAT molecules that are purposefully defined (programmed) by high-bias switching within the honeycomb lattice. Within such a unit the low-bias switching can be triggered and accessed by single-point measurements on a single TAT molecule, demonstrating up to 9 and 19 distinguishable states in a dyad and a tetrad of coupled molecules, respectively. High experimental control over the desired state, owing to bias-dependent hierarchical switching and pronounced switching directionality, as well as full reversibility, make this system particularly appealing, paving the way to design complex molecule-based memory systems.
RESUMEN
Intra- and intermolecular interactions are dominating chemical processes, and their concerted interplay enables complex nonequilibrium states like life. While the responsible basic forces are typically investigated spectroscopically, a conductance measurement to probe and control these interactions in a single molecule far out of equilibrium is reported here. Specifically, by separating macroscopic metal electrodes, two π-conjugated, bridge-connected porphyrin decks are peeled off on one side, but compressed on the other side due to the covalent mechanical fixation. We observe that the conductance response shows an exceptional exponential rise by two orders of magnitude in individual breaking events during the stretching. Theoretical studies atomistically explain the measured conductance behavior by a mechanically activated increase in through-bond transport and a simultaneous strengthening of through-space coupling. Our results not only reveal the various interacting intramolecular transport channels in a molecular set of levers, but also the molecules' potential to serve as molecular electro-mechanical sensors and switches.
RESUMEN
The possibility to study quantum interference phenomena at ambient conditions is an appealing feature of molecular electronics. By connecting two porphyrins in a cofacial cyclophane, we create an attractive platform for mechanically controlling electric transport through the intramolecular extent of π-orbital overlap of the porphyrins facing each other and through the angle of xanthene bridges with regard to the porphyrin planes. We analyze theoretically the evolution of molecular configurations in the pulling process and the corresponding changes in electric conduction by combining density functional theory (DFT) with Landauer scattering theory of phase-coherent elastic transport. Predicted conductances during the stretching process show order of magnitude variations caused by two robust destructive quantum interference features that span through the whole electronic gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Mechanically-controlled break junction (MCBJ) experiments at room temperature verify the mechanosensitive response of the molecular junctions. During the continuous stretching of the molecule, they show conductance variations of up to 1.5 orders of magnitude over single breaking events. Uncommon triple- and quadruple-frequency responses are observed in periodic electrode modulation experiments with amplitudes of up to 10 Å. This further confirms the theoretically predicted double transmission dips caused by the spatial and energetic rearrangement of molecular orbitals, with contributions from both through-space and through-bond transport.
RESUMEN
Quantum interference (QI) of electron waves passing through a single-molecule junction provides a powerful means to influence its electrical properties. Here, we investigate the correlation between substitution pattern, conductance, and mechanosensitivity in [2.2]paracyclophane (PCP)-based molecular wires in a mechanically controlled break junction experiment. The effect of the meta versus para connectivity in both the central PCP core and the phenyl ring connecting the terminal anchoring group is studied. We find that the meta-phenyl-anchored PCP yields such low conductance levels that molecular features cannot be resolved; in the case of para-phenyl-coupled anchoring, however, large variations in conductance values for modulations of the electrode separation occur for the pseudo-para-coupled PCP core, while this mechanosensitivity is absent for the pseudo-meta-PCP core. The experimental findings are interpreted in terms of QI effects between molecular frontier orbitals by theoretical calculations based on density functional theory and the Landauer formalism.
RESUMEN
The switching behavior of surface-supported molecular units excited by current, light, or mechanical forces is determined by the shape of the adsorption potential. The ability to tailor the energy landscape in which a molecule resides at a surface gives the possibility of imposing a desired response, which is of paramount importance for the realization of molecular electronic units. Here, by means of scanning tunneling microscopy, a triazatruxene (TAT) molecule on Ag(111) is studied, which shows a switching behavior characterized by transitions of the molecule between three states, and which is attributed to three energetically degenerate bonding configurations. Upon tunneling current injection, the system can be excited and continuously driven, showing a switching directionality close to 100%. Two surface enantiomers of TAT show opposite switching directions pointing at the chirality of the energy landscape of the adsorption potential as a key ingredient for directional switching. Further, it is shown that by tuning the tunneling parameters, the symmetry of the adsorption potential can be controllably adjusted, leading to a suppression of the directionality or an inversion of the switching direction. The findings represent a molecule-surface model system exhibiting unprecedented control of the shape of its adsorption potential.
RESUMEN
Motivated by a recent experiment [C. Guo et al., Proc. Natl. Acad. Sci. U. S. A. 113, 10785 (2016)], we carry out a theoretical study of electron transport through peptide-based single-molecule junctions. We analyze the pristine hepta-alanine and its functionalizations with a single tryptophan unit, which is placed in three different locations along the backbone. Contrary to expectations from the experiment on self-assembled monolayers, we find that insertion of tryptophan does not raise the electrical conductance and that the resulting peptides instead remain insulating in the framework of a coherent transport picture. The poor performance of these molecules as conductors can be ascribed to the strongly off-resonant transport and low electrode-molecule coupling of the frontier orbitals. Although the introduction of tryptophan increases the energy of the highest occupied molecular orbital (HOMO) of the peptides in the gas phase, the new HOMO states are localized on the tryptophan unit and therefore essentially do not contribute to coherent charge transport.