doi:10.1039/c6ra15477hengFerradas, Ruben R.Marques-Gonzalez, SantiagoOsorio, Henrry M.Ferrer, JaimeCea, PilarMilan, David C.Vezzoli, AndreaHiggins, Simon J.Nichols, Richard J.Low, Paul J.Garcia-Suarez, Victor M.Martin, SantiagoLow variability of single-molecule conductance assisted by bulky metal–molecule contactsART-2016-98377A detailed study of the trimethylsilylethynyl moiety, –C[triple bond, length as m-dash]CSiMe3 (TMSE), as an anchoring group in metal|molecule|metal junctions, using a combination of experiment and density functional theory is presented. It is shown that the TMSE anchoring group provides improved control over the molecule–substrate arrangement within metal|molecule|metal junctions, with the steric bulk of the methyl groups limiting the number of highly transmissive binding sites at the electrode surface, resulting in a single sharp peak in the conductance histograms recorded by both the in situ break junction and I(s) STM techniques. As a consequence of the low accessibility of the TMSE group to surface binding configurations of measurable conductance, only about 10% of gold break junction formation cycles result in the clear formation of molecular junctions in the experimental histograms. The DFT-computed transmission characteristics of junctions formed from the TMSE-contacted oligo(phenylene)ethynylene (OPE)-based molecules described here are dominated by tunneling effects through the highest-occupied molecular orbitals (HOMOs). This gives rise to similar conductance characteristics in these TMSE-contacted systems as found in low conductance-type junctions based on comparably structured OPE-derivatives with amine-contacts that also conduct through HOMO-based channels.2016http://zaguan.unizar.es/record/6093210.1039/c6ra15477hhttp://zaguan.unizar.es/record/60932oai:zaguan.unizar.es:60932info:eu-repo/grantAgreement/ES/DGA/E54info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-33198info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-50187-EXPinfo:eu-repo/grantAgreement/ES/MINECO/FIS2012-34858info:eu-repo/grantAgreement/ES/MINECO/RYC-2010-06053RSC Advances 6, 79 (2016), 75111-75121by-nchttp://creativecommons.org/licenses/by-nc/3.0/es/info:eu-repo/semantics/openAccess