60932 20200221144300.0 doi 10.1039/c6ra15477h sideral 98377 ART-2016-98377 eng Ferradas, Ruben R. Low variability of single-molecule conductance assisted by bulky metal–molecule contacts 2016 Access copy available to the general public Unrestricted A 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. info:eu-repo/grantAgreement/ES/DGA/E54 info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-33198 info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-50187-EXP info:eu-repo/grantAgreement/ES/MINECO/FIS2012-34858 info:eu-repo/grantAgreement/ES/MINECO/RYC-2010-06053 info:eu-repo/semantics/openAccess by-nc http://creativecommons.org/licenses/by-nc/3.0/es/ 3.108 2016 CHEMISTRY, MULTIDISCIPLINARY 59 / 166 = 0.355 2016 Q2 T2 0.889 2016 Chemistry (miscellaneous) 2016 Q1 Chemical Engineering (miscellaneous) 2016 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Marques-Gonzalez, Santiago Osorio, Henrry M. Ferrer, Jaime (orcid)0000-0002-4729-9578 Cea, Pilar Universidad de Zaragoza Milan, David C. Vezzoli, Andrea Higgins, Simon J. Nichols, Richard J. Low, Paul J. Garcia-Suarez, Victor M. (orcid)0000-0001-9193-3874 Martin, Santiago Universidad de Zaragoza 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 6, 79 (2016), 75111-75121 RSC ADVANCES RSC Advances 2046-2069 818895 http://zaguan.unizar.es/record/60932/files/texto_completo.pdf Versión publicada 113296 http://zaguan.unizar.es/record/60932/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:60932 articulos driver 2020-02-21-13:32:05 ARTICLE