The self-assembly and redox-properties of two viologen derivatives, N-hexyl-N 0 -(6-thiohexyl)-4,4 0 -bipyridinium bromide (HS-6V6-H) and N,N 0 -bis(6-thiohexyl)-4,4 0 -bipyridinium bromide (HS-6V6-SH), immobilized on Au(111)-(1 Â 1) macro-electrodes were investigated by cyclic voltammetry, surface enhanced infrared spectroscopy (SEIRAS) and in situ scanning tunneling microscopy (STM). Depending on the assembly conditions one could distinguish three different types of adlayers for both viologens: a low coverage disordered and an ordered ''striped'' phase of flat oriented molecules as well as a high coverage monolayer composed of tilted viologen moieties. Both molecules, HS-6V6-H and HS-6V6-SH, were successfully immobilized on Au(poly) nano-electrodes, which gave a well-defined redox-response in the lower pA-current range. An in situ STM configuration was employed to explore electron transport properties of single molecule junctions Au(T)|HS-6V6-SH(HS-6V6-H)|Au(S). The observed sigmoidal potential dependence, measured at variable substrate potential E S and at constant bias voltage (E T À E S ), was attributed to electronic structure changes of the viologen moiety during the one-electron reduction/re-oxidation process V 21 2 V 1d . Tunneling experiments in asymmetric, STM-based junctions Au(T)-S-6V6-H|Au(S) revealed current (i T )-voltage (E T ) curves with a maximum located at the equilibrium potential of the redox-process V 21 2 V 1d . The experimental i T À E T characteristics of the HS-6V6-H-modified tunneling junction were tentatively attributed to a sequential two-step electron transfer mechanism.
Summaryπ-Conjugation plays an important role in charge transport through single molecular junctions. We describe in this paper the construction of a mechanically controlled break-junction setup (MCBJ) equipped with a highly sensitive log I–V converter in order to measure ultralow conductances of molecular rods trapped between two gold leads. The current resolution of the setup reaches down to 10 fA. We report single-molecule conductance measurements of an anthracene-based linearly conjugated molecule (AC), of an anthraquinone-based cross-conjugated molecule (AQ), and of a dihydroanthracene-based molecule (AH) with a broken conjugation. The quantitative analysis of complementary current–distance and current–voltage measurements revealed details of the influence of π-conjugation on the single-molecule conductance.
Controlling the electrical conductance and in particular the occurrence of quantum interference in single-molecule junctions through gating effects, has potential for the realization of highperformance functional molecular devices. In this work, we used an electrochemically-gated, mechanically-controllable break junction technique to tune the electronic behaviour of thiophene-based molecular junctions that show destructive quantum interference (DQI) features. By varying the voltage applied to the electrochemical gate at room temperature, we
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