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ABSTRACT: We study the effects of molecular structure on the electronic transport and mechanical stability of single-molecule junctions formed with Au point contacts. Two types of linear conjugated molecular wires are compared: those functionalized with methylsulfide or amine aurophilic groups at (1) both or (2) only one of its phenyl termini. Using scanning tunneling and atomic force microscope break-junction techniques, the conductance of mono- and di-functionalized molecular wires and its dependence on junction elongation and rupture forces were studied. Charge transport through mono-functionalized wires is observed when the molecular bridge is coupled through a S-Au donor-acceptor bond on one end and a relatively weak Au-π interaction on the other end. For mono-functionalized molecular wires, junctions can be mechanically stabilized by installing a second aurophilic group at the meta-position that, however, does not in itself contribute to charge transport. These results reveal the important interplay between electronic coupling through metal-π interactions and quantum mechanical effects introduced by chemical substitution on the conjugated system. This study affords a strategy to deterministically tune the electrical and mechanical properties through molecular wires.
Journal of the American Chemical Society 11/2012; · 9.91 Impact Factor
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ABSTRACT: Making contact to a quantum dot: Single quantum-dot electronic circuits are fabricated by wiring atomically precise metal chalcogenide clusters with conjugated molecular connectors. These wired clusters can couple electronically to nanoscale electrodes and be tuned to control the charge-transfer characteristics.
Angewandte Chemie International Edition 11/2012; · 13.45 Impact Factor
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ABSTRACT: We characterize electron transport across Au-molecule-Au junctions of heterogeneous carboxyl and methyl sulfide terminated saturated and conjugated molecules. Low-bias conductance measurements are performed using the scanning tunneling microscopy based break-junction technique in the presence of solvents and at room temperature. For a series of alkanes with 1-4 carbon atoms in the hydrocarbon chain, our results show an exponential decrease in conductance with increasing molecule length characterized by a decay constant of 0.9 ± 0.1 per methylene group. Control measurements in pH 11 solutions and with COOMe terminations suggest that the carboxylic acid group binds through the formation of a COO(-)-Au bond. Simultaneous measurements of conductance and force across these junctions yield a rupture force of 0.6 ± 0.1 nN, comparable to that required to rupture a Au-SMe bond. By establishing reliable, in situ junction formation, these experiments provide a new approach to probe electronic properties of carboxyl groups at the single molecule level.
Physical Chemistry Chemical Physics 07/2012; 14(40):13841-5. · 3.57 Impact Factor
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ABSTRACT: Electronic factors in molecules such as quantum interference and cross-conjugation can lead to dramatic modulation and suppression of conductance in single-molecule junctions. Probing such effects at the single-molecule level requires simultaneous measurements of independent junction properties, as conductance alone cannot provide conclusive evidence of junction formation for molecules with low conductivity. Here, we compare the mechanics of the conducting para-terminated 4,4'-di(methylthio)stilbene and moderately conducting 1,2-bis(4-(methylthio)phenyl)ethane to that of insulating meta-terminated 3,3'-di(methylthio)stilbene single-molecule junctions. We simultaneously measure force and conductance across single-molecule junctions and use force signatures to obtain independent evidence of junction formation and rupture in the meta-linked cross-conjugated molecule even when no clear low-bias conductance is measured. By separately quantifying conductance and mechanics, we identify the formation of atypical 3,3'-di(methylthio)stilbene molecular junctions that are mechanically stable but electronically decoupled. While theoretical studies have envisaged many plausible systems where quantum interference might be observed, our experiments provide the first direct quantitative study of the interplay between contact mechanics and the distinctively quantum mechanical nature of electronic transport in single-molecule junctions.
Nano Letters 02/2012; 12(3):1643-7. · 13.20 Impact Factor
