Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions

Supramolecular wires are created in a confined nanoscale junction by using metalloporphyrin coordination chemistry in a similar fashion to that found in bacteria nanowires. Slight chemical changes in the axial ligands and in the porphyrin ring determine the exact final supramolecular scaffold, which...

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Autores: Aragonès, Albert C., Martín-Rodríguez, Alejandro, Aravena, Daniel, Puigmartí-Luis, Josep, Amabilino, David B., Aliaga-Alcalde, Núria, González-Campo, Arántzazu, Ruiz Sabín, Eliseo, Díez Pérez, Ismael
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2020
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/200204
Acceso en línea:https://hdl.handle.net/2445/200204
Access Level:acceso abierto
Palabra clave:Teoria del funcional de densitat
Electrònica molecular
Porfirines
Density functionals
Molecular electronics
Porphyrins
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spelling Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular InteractionsAragonès, Albert C.Martín-Rodríguez, AlejandroAravena, DanielPuigmartí-Luis, JosepAmabilino, David B.Aliaga-Alcalde, NúriaGonzález-Campo, ArántzazuRuiz Sabín, EliseoDíez Pérez, IsmaelTeoria del funcional de densitatElectrònica molecularPorfirinesDensity functionalsMolecular electronicsPorphyrinsSupramolecular wires are created in a confined nanoscale junction by using metalloporphyrin coordination chemistry in a similar fashion to that found in bacteria nanowires. Slight chemical changes in the axial ligands and in the porphyrin ring determine the exact final supramolecular scaffold, which defines the electron pathway along the supramolecular wire. Nature has developed supramolecular constructs to deliver outstanding charge-transport capabilities using metalloporphyrin-based supramolecular arrays. Herein we incorporate simple, naturally inspired supramolecular interactions via the axial complexation of metalloporphyrins into the formation of a single-molecule wire in a nanoscale gap. Small structural changes in the axial coordinating linkers result in dramatic changes in the transport properties of the metalloporphyrin-based wire. The increased flexibility of a pyridine-4-yl-methanethiol ligand due to an extra methyl group, as compared to a more rigid 4-pyridinethiol linker, allows the pyridine-4-yl-methanethiol ligand to adopt an unexpected highly conductive stacked structure between the two junction electrodes and the metalloporphyrin ring. DFT calculations reveal a molecular junction structure composed of a shifted stack of the two pyridinic linkers and the metalloporphyrin ring. In contrast, the more rigid 4-mercaptopyridine ligand presents a more classical lifted octahedral coordination of the metalloporphyrin metal center, leading to a longer electron pathway of lower conductance. This works opens to supramolecular electronics, a concept already exploited in natural organisms.Wiley-VCH2023202320202023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersion9 p.application/pdfhttps://hdl.handle.net/2445/200204Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésReproducció del document publicat a: https://doi.org/10.1002/anie.202007237Angewandte Chemie, 2020, vol. 59, num. 43, p. 19193-19201https://doi.org/10.1002/anie.202007237(c) Aragonès, Albert C., 2020info:eu-repo/semantics/openAccessoai:recercat.cat:2445/2002042026-05-29T05:05:01Z
dc.title.none.fl_str_mv Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions
title Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions
spellingShingle Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions
Aragonès, Albert C.
Teoria del funcional de densitat
Electrònica molecular
Porfirines
Density functionals
Molecular electronics
Porphyrins
title_short Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions
title_full Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions
title_fullStr Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions
title_full_unstemmed Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions
title_sort Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions
dc.creator.none.fl_str_mv Aragonès, Albert C.
Martín-Rodríguez, Alejandro
Aravena, Daniel
Puigmartí-Luis, Josep
Amabilino, David B.
Aliaga-Alcalde, Núria
González-Campo, Arántzazu
Ruiz Sabín, Eliseo
Díez Pérez, Ismael
author Aragonès, Albert C.
author_facet Aragonès, Albert C.
Martín-Rodríguez, Alejandro
Aravena, Daniel
Puigmartí-Luis, Josep
Amabilino, David B.
Aliaga-Alcalde, Núria
González-Campo, Arántzazu
Ruiz Sabín, Eliseo
Díez Pérez, Ismael
author_role author
author2 Martín-Rodríguez, Alejandro
Aravena, Daniel
Puigmartí-Luis, Josep
Amabilino, David B.
Aliaga-Alcalde, Núria
González-Campo, Arántzazu
Ruiz Sabín, Eliseo
Díez Pérez, Ismael
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Teoria del funcional de densitat
Electrònica molecular
Porfirines
Density functionals
Molecular electronics
Porphyrins
topic Teoria del funcional de densitat
Electrònica molecular
Porfirines
Density functionals
Molecular electronics
Porphyrins
description Supramolecular wires are created in a confined nanoscale junction by using metalloporphyrin coordination chemistry in a similar fashion to that found in bacteria nanowires. Slight chemical changes in the axial ligands and in the porphyrin ring determine the exact final supramolecular scaffold, which defines the electron pathway along the supramolecular wire. Nature has developed supramolecular constructs to deliver outstanding charge-transport capabilities using metalloporphyrin-based supramolecular arrays. Herein we incorporate simple, naturally inspired supramolecular interactions via the axial complexation of metalloporphyrins into the formation of a single-molecule wire in a nanoscale gap. Small structural changes in the axial coordinating linkers result in dramatic changes in the transport properties of the metalloporphyrin-based wire. The increased flexibility of a pyridine-4-yl-methanethiol ligand due to an extra methyl group, as compared to a more rigid 4-pyridinethiol linker, allows the pyridine-4-yl-methanethiol ligand to adopt an unexpected highly conductive stacked structure between the two junction electrodes and the metalloporphyrin ring. DFT calculations reveal a molecular junction structure composed of a shifted stack of the two pyridinic linkers and the metalloporphyrin ring. In contrast, the more rigid 4-mercaptopyridine ligand presents a more classical lifted octahedral coordination of the metalloporphyrin metal center, leading to a longer electron pathway of lower conductance. This works opens to supramolecular electronics, a concept already exploited in natural organisms.
publishDate 2020
dc.date.none.fl_str_mv 2020
2023
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/200204
url https://hdl.handle.net/2445/200204
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.1002/anie.202007237
Angewandte Chemie, 2020, vol. 59, num. 43, p. 19193-19201
https://doi.org/10.1002/anie.202007237
dc.rights.none.fl_str_mv (c) Aragonès, Albert C., 2020
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Aragonès, Albert C., 2020
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 9 p.
application/pdf
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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