Solvent dependence of the single molecule conductance of oligoyne-based molecular wires
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 fo...
| Autores: | , , , , , , , , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2016 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/148208 |
| Acceso en línea: | http://hdl.handle.net/10261/148208 |
| Access Level: | acceso abierto |
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| dc.title.none.fl_str_mv |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires |
| title |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires |
| spellingShingle |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires Milan, David C. |
| title_short |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires |
| title_full |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires |
| title_fullStr |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires |
| title_full_unstemmed |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires |
| title_sort |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wires |
| dc.creator.none.fl_str_mv |
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. |
| author |
Milan, David C. |
| author_facet |
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. |
| author_role |
author |
| author2 |
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. |
| author2_role |
author author author author author author author author author author author author author author author |
| dc.contributor.none.fl_str_mv |
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 Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| description |
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. |
| publishDate |
2016 |
| dc.date.none.fl_str_mv |
2016 2017 2017 2017 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Postprint info:eu-repo/semantics/acceptedVersion |
| format |
article |
| status_str |
acceptedVersion |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10261/148208 |
| url |
http://hdl.handle.net/10261/148208 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.relation.none.fl_str_mv |
#PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# 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 https://doi.org/10.1021/acs.jpcc.5b08877 Sí |
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info:eu-repo/semantics/openAccess |
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openAccess |
| dc.publisher.none.fl_str_mv |
American Chemical Society |
| publisher.none.fl_str_mv |
American Chemical Society |
| dc.source.none.fl_str_mv |
reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC instname:Consejo Superior de Investigaciones Científicas (CSIC) |
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Consejo Superior de Investigaciones Científicas (CSIC) |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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| _version_ |
1869422999201906688 |
| spelling |
Solvent dependence of the single molecule conductance of oligoyne-based molecular wiresMilan, David C.Al-Owaedi, Oday A.Oerthel, Marie-ChristineMarqués-González, SantiagoBrooke, Richard J.Bryce, Martin R.Cea, PilarFerrer, JaimeHiggins, Simon J.Lambert, Colin J.Low, Paul J.Manrique, D. Zs.Martín, SantiagoNichols, Richard J.Schwarzacher, WaltherGarcía-Suárez, Víctor M.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.D.C.M., S.J.H., R.J.N., P.J.L., and S.M-G. thank EPSRC for funding (EPSRC Grants EP/K007785/1, EP/H035184/1, and EP/K007548/1). P.J.L. holds an ARC Future Fellowship (FT120100073) and gratefully acknowledges funding for this work from the ARC (DP140100855). C.J.L. and O.A.A. acknowledge financial support from the Ministry of Higher Education and Scientific Research of Iraq. V.M.G.-S. thanks the Spanish Ministerio de Economıa y Competitividad for a Ramoń y Cajal fellowship (RYC-2010-06053). J.F. and V.M.G.-S. acknowledge financial support from the Spanish MICINN Grant FIS2012-34858 and the Marie Curie Network MOLESCO. They also acknowledge the supercomputing facility CESGA where part of the calculations was carried out. P.C. and S.M. are grateful for financial assistance from Ministerio de Economia y Competitividad from Spain in the framework of the project CTQ2012-33198 as well as the award of the CTQ2013-50187-EXP grant. P.C and S.M. thank the DGA and Fondos FEDER for funding for the Platon research group. S.M. thanks the Ministerio de Educacion of Spain for financial support in the framework of the Campus de Excelencia Internacional, CEI Iberus. M.R.B. and C.J.L. acknowledge funding from the EU through the FP7 ITN MOLESCO (Project Number 212942).Peer ReviewedAmerican Chemical SocietyMinistry of Higher Education and Scientific Research (Iraq)Australian Research CouncilEngineering and Physical Sciences Research Council (UK)Centro de Supercomputación de GaliciaEuropean CommissionMinisterio de Educación (España)Ministerio de Economía y Competitividad (España)Ministerio de Ciencia e Innovación (España)Diputación General de AragónConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2017201720162017info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/148208reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2013-50187-EXPinfo:eu-repo/grantAgreement/EC/FP7/212942info:eu-repo/grantAgreement/EC/FP7/606728https://doi.org/10.1021/acs.jpcc.5b08877Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1482082026-05-22T06:33:51Z |
| score |
15,81155 |