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n-5H self-assembling monolayers were prepared by Incubating freshly annealed epitaxial Au(111) surfaces (Molecular Imaging, Phoenix, AZ) in 1-mM solutions of toluene or ethanol for 12 to 14 hours. C12d was synthesized as described elsewhere (23). For insertion of the alkane dithiols, the films were rinsed and then incubated in 1-mM dithiol solutions for 8 hours. PETB was prepared as described elsewhere (10). The insertion of PETB was achieved by placing the rinsed Au(111) film in a 0.5-mM solution of the molecule in distilled tetrahydrofuran and ammonium hydroxide (10 μl) for 30 min in an inert particulatefree glove box. Gold NPs (1.5 nm in diameter) were prepared as described in (21). Molecules studied with the gold NPs attachment were prepared by rinsing of the dithiol-inserted film, followed by incubation in a solution of methylene chloride or tetrahydrofuran (THF) (1 mg of NPs per 30 ml). All films were thoroughly rinsed in toluene (and in methylene chloride if necessary) before measurement. Conducting AFM and STM experiments were performed in liquid cells under toluene in a controlled Ar atmosphere, using a PicoSPM microscope (Molecular Imaging). The set point bias and tunnel currents were -1.00 V and 12 pA, -0.75 V and 18 pA, 0.75 V and 6.5 pA, -1.0 V and 15.0 pA, -1.0 V and 7. 5 pA, and -1.0 V and 15.0 pA for C8d, C10d, C12d, C12d-Au, PETB, and PETB-Au, respectively.
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The height of the gold NPs was smaller than might be expected if the conductivity of the PETB molecular wire were much larger, on a per-carbon basis, than that of the surrounding alkanethiols. However, experiments (10) on single molecules with attached NPs show that this is not the case.
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0037506957
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See the supporting information on Science Online.
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0038520954
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Supported by a Nanoscale Interdisciplinary Research Teams award of NSF. We thank D. Gust, A. Moore, T. Moore, O. F. Sankey, J. Tomfohr, X. Zarate, G. Kada, R. Tsui, and H. Goronkin for helpful discussions and J. Robinson for assistance with data analysis.
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