Thin layers of cobalt and ruthenium polypyridyl-oligomers with thicknesses between 2 and 8 nm were deposited on gold by electrochemical reduction of diazonium salts. A scanning tunneling microscope was used to create single-molecule junctions (SMJs). The charge transport properties of the Au-[Co(tpy)2]n-Au (n = 1-4) SMJs do not depend markedly on the oligomer length, have an extremely low attenuation factor (β ∼ 0.19 nm-1), and do not show a thickness-dependent transition between two mechanisms. Resonant charge transport is proposed as the main transport mechanism. The SMJ conductance decreases by 1 order of magnitude upon changing the metal from Co to Ru. In Au-[Ru(tpy)2]n-Au and Au-[Ru(bpy)3]n-Au SMJs, a charge transport transition from direct tunneling to hopping is evidenced by a break in the length-dependent β-plot. The three different mechanisms observed are a clear molecular signature on transport in SMJs. Most importantly, these results are in good agreement with those obtained on large-area molecular junctions.
Keywords: diazonium electroreduction; hopping; molecular electronics; single-molecule junctions; tunneling.