We demonstrate a generic synthetic approach to oligophenylenevinylene (OPV) derivative molecules
with a molecular length of up to 12 nm and a relatively free choice of end group that can attach to
different electrodes such as metallic gold or potentially transition metal oxide semiconductors. OPVs
containing 3–19 phenyl units were synthesised by step wise HWE-reactions of a bifunctional
OPV-monomer which allowed for complete control of the sizes of the OPVs. Workup and analysis (1Hand
13C-NMR, mass spectrometry and size exclusion chromatography) of each step ensured a high
purity of the final products. Final end group functionalities of the OPVs were introduced either as the
first step (alcohol) or the last step (thioacetate). We further demonstrate a fabrication method for well
defined nanogap electrode devices based on silicon-on-insulator technology, featuring a gap distance of
down to 9 nm. Assembling the OPV derivatives onto these devices enabled preliminary investigations of
their low-temperature transport properties, revealing a pronounced non-linear current–voltage
characteristic at 4.2 K. We studied the electronic states of the molecule by Density Functional Theory
(DFT) in order to show the effect of the ligands and of the gold contacts. By using the results of the
DFT calculations in a non-equilibrium Green’s function model, the current–voltage characteristics of
OPVs have been analyzed, showing a good qualitative agreement with the experimental data.
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