2024-03-28T16:04:44Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1482082020-12-10T15:47:33Zcom_10261_28457com_10261_3com_10261_31col_10261_28462col_10261_284
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires
Milan, David C.
Al-Owaedi, Oday A.
Oerthel, Marie-Christine
Marqués-González, Santiago
Brooke, Richard J.
Bryce, Martin R.
Cea, Pilar
Ferrer, Jaime
Higgins, Simon J.
Lambert, Colin J.
Low, Paul J.
Manrique, D. Zs.
Martín, Santiago
Nichols, Richard J.
Schwarzacher, Walther
García-Suárez, Víctor M.
Ministry of Higher Education and Scientific Research (Iraq)
Australian Research Council
Engineering and Physical Sciences Research Council (UK)
Centro de Supercomputación de Galicia
European Commission
Ministerio de Educación (España)
Ministerio de Economía y Competitividad (España)
Ministerio de Ciencia e Innovación (España)
Diputación General de Aragón
The conductance and the decay of conductance as a function of molecular length within a homologous series of oligoynes, MeSi - (C≡C) - SiMe (n = 2, 3, 4, or 5), is shown to depend strongly on the solvent medium. Single molecule junction conductance measurements have been made with the I(s) method for each member of the series MeSi - (C≡C) - SiMe (n = 2, 3, 4, and 5) in mesitylene (MES), 1,2,4-trichlorobenzene (TCB), and propylene carbonate (PC). In mesitylene, a lower conductance is obtained across the whole series with a higher length decay (β ≈ 1 nm). In contrast, measurements in 1,2,4-trichlorobenzene and propylene carbonate give higher conductance values with lower length decay (β ≈ 0.1 and 0.5 nm respectively). This behavior is rationalized through theoretical and computational investigations, where β values are found to be higher when the contact Fermi energies are close to the middle of the HOMO-LUMO gap but decrease as the Fermi energies approach resonance with either the occupied or unoccupied frontier orbitals. The different conductance and β values between MES, PC, and TCB have been further explored using DFT-based models of the molecular junction, which include solvent molecules interacting with the oligoyne backbone. Good agreement between the experimental results and these >solvated> junction models is achieved, giving new insights into how solvent can influence charge transport in oligoyne-based single molecule junctions.
2017-04-10T10:39:39Z
2017-04-10T10:39:39Z
2016
2017-04-10T10:39:40Z
artículo
Journal of Physical Chemistry C 120(29): 15666-15674 (2016)
http://hdl.handle.net/10261/148208
10.1021/acs.jpcc.5b08877
http://dx.doi.org/10.13039/501100007335
http://dx.doi.org/10.13039/501100000923
http://dx.doi.org/10.13039/501100000266
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/501100004837
eng
Postprint
https://doi.org/10.1021/acs.jpcc.5b08877
Sí
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2013-50187-EXP
info:eu-repo/grantAgreement/EC/FP7/212942
info:eu-repo/grantAgreement/EC/FP7/606728
openAccess
American Chemical Society