Abstract
The conductance of molecular junctions formed ofN,N′-bis(n-thioalkyl)-4,4′-bipyridinium bromides or alkanedithiols between a gold (Au) scanning tunnelling microscope tip and aAu(111)-(1 × 1) electrode has been studied at electrified solid/liquid interfaces. A statistical analysis based onlarge sets of individual current–distance traces was applied to obtain the electrical conductanceof single junctions. The one-electron reduction of the viologen moiety from the dicationV2+ to the radical cation state gives rise to a 50% increase of the junction conductance. Increasingthe length of the alkyl spacer units leads to a tunnelling decay constantβCH2 = 5.9–6.1 nm−1. This value issignificantly lower than βCH2 = 8.2 nm−1 estimated for molecular junctions of alkanedithiols. The difference is attributed toconformational changes within the two junctions. The contact conductance was estimated to10 µS.
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