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So-called bottom-up fabrication methods aim to assemble and integrate molecular components exhibiting specific functions into electronic devices that are orders of magnitude smaller than can
be fabricated by lithographic techniques. Fundamental to the success of the bottom-up approach is the ability to control electron transport across molecular components. Organic molecules containing redox centres—chemical species whose oxidation
number, and hence electronic structure, can be changed
reversibly—support resonant tunnelling1,2 and display promising functional behaviour when sandwiched as molecular layers between electrical contacts3,4, but their integration into more
complex assemblies remains challenging. For this reason, functionalized metal nanoparticles have attracted much interest5–7: they exhibit single-electron characteristics8–10 (such as quantized
capacitance charging) and can be organized11–13 through simple self-assembly methods into well ordered structures, with the nanoparticles at controlled locations. Here we report scanning
tunnelling microscopy measurements showing that organic molecules containing redox centres can be used to attach metal nanoparticles to electrode surfaces and so control the electron
transport between them. Our system consists of gold nanoclusters a few nanometres across and functionalized with polymethylene chains that carry a central, reversibly reducible bipyridinium moiety14,15. We expect that the ability to electronically contact metal nanoparticles via redox-active molecules, and to alter profoundly their tunnelling properties by charge injection into
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