A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)

Autores
O'Boyle, Noel M.; Albrecht, Tim; Murgida, Daniel Horacio; Cassidy, Lynda; Ulstrup, Jens; Vos, Johannes G.
Año de publicación
2007
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We present a density functional theory (DFT) study of an osmium polypyridyl complex adsorbed on Au(111). The osmium polypyridyl complex [Os(bpy)2(P0P)Cl]n+ [bpy is 2,2'-bipyridine, P0P is 4,4'-bipyridine, n = 1 for osmium(II), and n = 2 for osmium(III)] is bound to the surface through the free nitrogen of the P0P ligand. The calculations illuminate electronic properties relevant to recent comprehensive characterization of this class of osmium complexes by electrochemistry and electrochemical scanning tunneling microscopy. The optimized structures for the compounds are in close agreement with crystallographic structures reported in the literature. Oxidation of the complex has little effect on these structural features, but there is a substantial reordering of the electronic energy levels with corresponding changes in the electron density. Significantly, the highest occupied molecular orbital shifts from the metal center to the P0P ligand. The surface is modeled by a cluster of 28 gold atoms and gives a good description of the effect of immobilization on the electronic properties of the complexes. The results show that the coupling between the immobilized complex and the gold surface involves electronic polarization at the adsorbate/substrate interface rather than the formation of a covalent bond. However, the cluster is too small to fully represent bulk gold with the result that, contrary to what is experimentally observed, the DFT calculation predicts that the gold surface is more easily oxidized than the osmium(II) complex.
Fil: O'Boyle, Noel M.. Dublin City University; Irlanda
Fil: Albrecht, Tim. Technical University of Denmark; Dinamarca
Fil: Murgida, Daniel Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Technische Universita¨t Berlin; Alemania
Fil: Cassidy, Lynda. Dublin City University; Irlanda
Fil: Ulstrup, Jens. Technical University of Denmark; Dinamarca
Fil: Vos, Johannes G.. Dublin City University; Irlanda
Materia
OSMIUM COMPLEXES
ELECTRON TRANSFER
RAMAN
DFT CALCULATIONS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/103856
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/103856
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)O'Boyle, Noel M.Albrecht, TimMurgida, Daniel HoracioCassidy, LyndaUlstrup, JensVos, Johannes G.OSMIUM COMPLEXESELECTRON TRANSFERRAMANDFT CALCULATIONShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We present a density functional theory (DFT) study of an osmium polypyridyl complex adsorbed on Au(111). The osmium polypyridyl complex [Os(bpy)2(P0P)Cl]n+ [bpy is 2,2'-bipyridine, P0P is 4,4'-bipyridine, n = 1 for osmium(II), and n = 2 for osmium(III)] is bound to the surface through the free nitrogen of the P0P ligand. The calculations illuminate electronic properties relevant to recent comprehensive characterization of this class of osmium complexes by electrochemistry and electrochemical scanning tunneling microscopy. The optimized structures for the compounds are in close agreement with crystallographic structures reported in the literature. Oxidation of the complex has little effect on these structural features, but there is a substantial reordering of the electronic energy levels with corresponding changes in the electron density. Significantly, the highest occupied molecular orbital shifts from the metal center to the P0P ligand. The surface is modeled by a cluster of 28 gold atoms and gives a good description of the effect of immobilization on the electronic properties of the complexes. The results show that the coupling between the immobilized complex and the gold surface involves electronic polarization at the adsorbate/substrate interface rather than the formation of a covalent bond. However, the cluster is too small to fully represent bulk gold with the result that, contrary to what is experimentally observed, the DFT calculation predicts that the gold surface is more easily oxidized than the osmium(II) complex.Fil: O'Boyle, Noel M.. Dublin City University; IrlandaFil: Albrecht, Tim. Technical University of Denmark; DinamarcaFil: Murgida, Daniel Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Technische Universita¨t Berlin; AlemaniaFil: Cassidy, Lynda. Dublin City University; IrlandaFil: Ulstrup, Jens. Technical University of Denmark; DinamarcaFil: Vos, Johannes G.. Dublin City University; IrlandaAmerican Chemical Society2007-01-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/103856O'Boyle, Noel M.; Albrecht, Tim; Murgida, Daniel Horacio; Cassidy, Lynda; Ulstrup, Jens; et al.; A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111); American Chemical Society; Inorganic Chemistry; 46; 1; 8-1-2007; 117-1240020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic060903einfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic060903einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:54:15Zoai:ri.conicet.gov.ar:11336/103856instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:54:15.488CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)
title A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)
spellingShingle A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)
O'Boyle, Noel M.
OSMIUM COMPLEXES
ELECTRON TRANSFER
RAMAN
DFT CALCULATIONS
title_short A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)
title_full A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)
title_fullStr A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)
title_full_unstemmed A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)
title_sort A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)
dc.creator.none.fl_str_mv O'Boyle, Noel M.
Albrecht, Tim
Murgida, Daniel Horacio
Cassidy, Lynda
Ulstrup, Jens
Vos, Johannes G.
author O'Boyle, Noel M.
author_facet O'Boyle, Noel M.
Albrecht, Tim
Murgida, Daniel Horacio
Cassidy, Lynda
Ulstrup, Jens
Vos, Johannes G.
author_role author
author2 Albrecht, Tim
Murgida, Daniel Horacio
Cassidy, Lynda
Ulstrup, Jens
Vos, Johannes G.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv OSMIUM COMPLEXES
ELECTRON TRANSFER
RAMAN
DFT CALCULATIONS
topic OSMIUM COMPLEXES
ELECTRON TRANSFER
RAMAN
DFT CALCULATIONS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We present a density functional theory (DFT) study of an osmium polypyridyl complex adsorbed on Au(111). The osmium polypyridyl complex [Os(bpy)2(P0P)Cl]n+ [bpy is 2,2'-bipyridine, P0P is 4,4'-bipyridine, n = 1 for osmium(II), and n = 2 for osmium(III)] is bound to the surface through the free nitrogen of the P0P ligand. The calculations illuminate electronic properties relevant to recent comprehensive characterization of this class of osmium complexes by electrochemistry and electrochemical scanning tunneling microscopy. The optimized structures for the compounds are in close agreement with crystallographic structures reported in the literature. Oxidation of the complex has little effect on these structural features, but there is a substantial reordering of the electronic energy levels with corresponding changes in the electron density. Significantly, the highest occupied molecular orbital shifts from the metal center to the P0P ligand. The surface is modeled by a cluster of 28 gold atoms and gives a good description of the effect of immobilization on the electronic properties of the complexes. The results show that the coupling between the immobilized complex and the gold surface involves electronic polarization at the adsorbate/substrate interface rather than the formation of a covalent bond. However, the cluster is too small to fully represent bulk gold with the result that, contrary to what is experimentally observed, the DFT calculation predicts that the gold surface is more easily oxidized than the osmium(II) complex.
Fil: O'Boyle, Noel M.. Dublin City University; Irlanda
Fil: Albrecht, Tim. Technical University of Denmark; Dinamarca
Fil: Murgida, Daniel Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Technische Universita¨t Berlin; Alemania
Fil: Cassidy, Lynda. Dublin City University; Irlanda
Fil: Ulstrup, Jens. Technical University of Denmark; Dinamarca
Fil: Vos, Johannes G.. Dublin City University; Irlanda
description We present a density functional theory (DFT) study of an osmium polypyridyl complex adsorbed on Au(111). The osmium polypyridyl complex [Os(bpy)2(P0P)Cl]n+ [bpy is 2,2'-bipyridine, P0P is 4,4'-bipyridine, n = 1 for osmium(II), and n = 2 for osmium(III)] is bound to the surface through the free nitrogen of the P0P ligand. The calculations illuminate electronic properties relevant to recent comprehensive characterization of this class of osmium complexes by electrochemistry and electrochemical scanning tunneling microscopy. The optimized structures for the compounds are in close agreement with crystallographic structures reported in the literature. Oxidation of the complex has little effect on these structural features, but there is a substantial reordering of the electronic energy levels with corresponding changes in the electron density. Significantly, the highest occupied molecular orbital shifts from the metal center to the P0P ligand. The surface is modeled by a cluster of 28 gold atoms and gives a good description of the effect of immobilization on the electronic properties of the complexes. The results show that the coupling between the immobilized complex and the gold surface involves electronic polarization at the adsorbate/substrate interface rather than the formation of a covalent bond. However, the cluster is too small to fully represent bulk gold with the result that, contrary to what is experimentally observed, the DFT calculation predicts that the gold surface is more easily oxidized than the osmium(II) complex.
publishDate 2007
dc.date.none.fl_str_mv 2007-01-08
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/103856
O'Boyle, Noel M.; Albrecht, Tim; Murgida, Daniel Horacio; Cassidy, Lynda; Ulstrup, Jens; et al.; A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111); American Chemical Society; Inorganic Chemistry; 46; 1; 8-1-2007; 117-124
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/103856
identifier_str_mv O'Boyle, Noel M.; Albrecht, Tim; Murgida, Daniel Horacio; Cassidy, Lynda; Ulstrup, Jens; et al.; A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111); American Chemical Society; Inorganic Chemistry; 46; 1; 8-1-2007; 117-124
0020-1669
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic060903e
info:eu-repo/semantics/altIdentifier/doi/10.1021/ic060903e
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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