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Conductance of redox-active single molecular junctions: an electrochemical approach

Zhihai Li1, Ilya Pobelov1, Bo Han1, Thomas Wandlowski1,4, Alfred Błaszczyk2,5 and Marcel Mayor2,3

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The conductance of molecular junctions formed of N,N'-bis(n-thioalkyl)-4,4'-bipyridinium bromides or alkanedithiols between a gold (Au) scanning tunnelling microscope tip and a Au(111)-(1 × 1) electrode has been studied at electrified solid/liquid interfaces. A statistical analysis based on large sets of individual current–distance traces was applied to obtain the electrical conductance of single junctions. The one-electron reduction of the viologen moiety from the dication V2+ to the radical cation state \mathrm {V}^{+\bdot } gives rise to a 50% increase of the junction conductance. Increasing the length of the alkyl spacer units leads to a tunnelling decay constant βCH2 = 5.9–6.1 nm−1. This value is significantly lower than βCH2 = 8.2 nm−1 estimated for molecular junctions of alkanedithiols. The difference is attributed to conformational changes within the two junctions. The contact conductance was estimated to 10 µS.


PACS

73.63.-b Electronic transport in nanoscale materials and structures

82.45.Fk Electrodes

81.16.Be Chemical synthesis methods

82.45.Yz Nanostructured materials in electrochemistry

82.45.Gj Electrolytes

73.40.Gk Tunneling

Subjects

Surfaces, interfaces and thin films

Nanoscale science and low-D systems

Chemical physics and physical chemistry

Dates

Issue 4 (31 January 2007)

Received 19 August 2006, in final form 27 October 2006

Published 12 December 2006



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