Mechanical compression in cofacial porphyrin cyclophane pincers

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\u27 potential to serve as molecular electro-mechanical sensors and switches

Mechanical conductance tunability of a porphyrin–cyclophane single-molecule junction

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

Mechanical conductance tunability of a porphyrin–cyclophane single-molecule junction

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. This journal is QN/van der Zant La

Single-molecule transport of fullerene-based curcuminoids

We present experimental and theoretical studies of single-molecule conductance through nonplanar fullerocurcuminoid molecular dyads in ambient conditions using the mechanically controllable break junction technique. We show that molecular dyads with bare fullerenes form configurations with conductance features related to different transport channels within the molecules, as identified with filtering and clustering methods. The primary channel corresponds to charge transport through the methylthio-terminated backbone. Additional low-conductance channels involve one backbone side and the fullerene. In fullerenes with four additional equatorial diethyl malonate groups attached to them, the latter transport pathway is blocked. Density functional theory calculations corroborate the experimental observations. In combination with nonequilibrium green functions, the conductance values of the fullerocurcuminoid backbones are found to be similar to those of a planar curcuminoid molecule without a fullerene attached. In the nonplanar fullerocurcuminoid systems, the highest-conductance peak occurs partly through space, compensating for the charge delocalization loss present in the curcuminoid system

Observation of the Transverse Optical Plasmon in SmLa0.8Sr0.2CuO4-d

We present microwave and infrared measurements on SmLa0.8Sr0.2CuO4-d, which are direct evidence for the existence of a transverse optical plasma mode, observed as a peak in the c-axis optical conductivity. This mode appears as a consequence of the existence of two different intrinsic Josephson couplings between the CuO2 layers, one with a Sm2O2 block layer, and the other one with a (La,Sr)O block layer. From the frequencies and the intensities of the collective modes we determine the value of the compressibility of the two dimensional electron fluid in the copper oxygen planes.Comment: REVTeX, 4 pages, 5 eps-figures, PRL, in pres

C-axis Penetration Depth and Inter-layer Conductivity in the Thallium Based Cuprate Superconductors

The c-axis Josephson plasmon in optimally doped single-layer and bi-layer high Tc cuprates Tl2201 and Tl2212 have been investigated using infrared spectroscopy. We observed the plasma frequencies for these two compounds at 27.8 and 25.6 cm-1 respectively, which we interpret as a Josephson resonance across the TlO blocking layers. No maximum in the temperature dependence of the c-axis conductivity was observed below Tc, indicating that even in the superconducting state a coherent quasi-particle contribution to the c-axis conductivity is absent or very weak, in contrast to the behaviour of the ab-plane conductivity.Comment: 4 pages, 3 figure

Charge transport through a single molecule of trans-1-bis-diazofluorene [60]fullerene

et al.Fullerenes have attracted interest for their possible applications in various electronic, biological, and optoelectronic devices. However, for efficient use in such devices, a suitable anchoring group has to be employed that forms well-defined and stable contacts with the electrodes. In this work, we propose a novel fullerene tetramalonate derivate functionalized with trans-1 4,5-diazafluorene anchoring groups. The conductance of single-molecule junctions, investigated in two different setups with the mechanically controlled break junction technique, reveals the formation of molecular junctions at three conductance levels. We attribute the conductance peaks to three binding modes of the anchoring groups to the gold electrodes. Density functional theory calculations confirm the existence of multiple binding configurations and calculated transmission functions are consistent with experimentally determined conductance values.The work at TUDelft was supported by the EU through an advanced ERC grant (Mols@Mols); device fabrication was done at the Kavli Nanolab at Delft. The work at University of Chile was supported by Fondecyt Regular Project 1161775 (M.S. and J.L.M.), Fondecyt Regular Project 1140770, EU RISE (DAFNEOX) project SEP-210165479 (D.D.), and CONICYT/Fondecyt Postdoctoral Project 3150674 (C.G.C.). D.A. thanks CONICYT + PAI ‘Concurso nacional de apoyo al retorno de investigadores/as desde el extranjero, convocatoria 2014 82140014’ for financial support. Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02). L.E. thanks the National Science Foundation [grant CHE-1408865] and the PREM Program [grant DMR-1205302] as well as the Robert A. Welch Foundation [grant AH-0033] for generous financial support.Peer reviewe

Temperature Gating of the Ring-Opening Process in Diarylethene Molecular Switches

The ring-opening process in diarylethene molecular switches is suppressed with decreasing temperature, leading to the complete absence of the photoreaction below a cutoff temperature. By contrast, the reverse ring-closure process shows no significant temperature dependence above 115 K. Reversibility of the photoprocesses can be thus controlled by temperature (see figure)