Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules

Autores
Faraggi, Marisa Noemi; Jiang, Nan; Gonzalez Lakuntza, Nora; Langner, Alexander; Stepanow, Sebastian; Kern, Klaus; Arnau, Andres
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The geometric and electronic structure of two structurally similar metal–organic networks grown on the Au(111) surface is investigated by scanning tunnelling microscopy (STM) and spectroscopy (STS) combined with density functional theory (DFT) calculations. The networks are composed of (i) F4TCNQ (C12F4N4, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquino–dimethane) molecules and Au adatoms segregated from the pristine metal surface, and (ii) TCNQ (C12H4N4, 7,7,8,8-tetracyanoquinodimethane) and codeposited Mn atoms. In both cases, the strong electron acceptor character of the molecules results in metal–to-ligand charge transfer to the lowest unoccupied molecular orbital (LUMO). The amount of electrons donated from the 4-fold coordinated Mn atoms to TCNQ is higher compared to the 2-fold coordinated Au adatoms to F4TCNQ. This behavior is reflected in the appearance of distinct spectral features in STS data in the energy region close to the Fermi level resulting from the intricate interplay between surface states, adatom states, and molecular orbitals. These observations are consistent with a picture in which the LUMO of the TCNQ acceptor molecule hybridizes with Mn and Au substrate metal states becoming practically filled, while the LUMO of F4TCNQ is only partially filled despite being the stronger electron acceptor. Our results reveal the importance of the type of bonding between the strong acceptor and the metal center (Au or Mn) as well as its coordination in the determination of the charge transfer to the adlayer, which is important for its electronic properties.
Fil: Faraggi, Marisa Noemi. Consejo Nacional de Investigaciónes Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Astronomía y Física del Espacio. - Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Astronomía y Física del Espacio; Argentina. Donostia International Physics Center; España
Fil: Jiang, Nan. Max-planck-institut Fu R Festkorperforschung; Alemania
Fil: Gonzalez Lakuntza, Nora. Donostia International Physics Center; España
Fil: Langner, Alexander. Max-planck-institut Fu R Festkorperforschung; Alemania
Fil: Stepanow, Sebastian. Max-planck-institut Fu R Festkorperforschung; Alemania
Fil: Kern, Klaus. Max-planck-institut Fur Festkorperforschun; Alemania
Fil: Arnau, Andres. Max-planck-institut Fur Festkorperforschun; Alemania
Materia
Surface
Network
Molecule
Acceptor
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:11336/19515
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/19515
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor MoleculesFaraggi, Marisa NoemiJiang, NanGonzalez Lakuntza, NoraLangner, AlexanderStepanow, SebastianKern, KlausArnau, AndresSurfaceNetworkMoleculeAcceptorhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The geometric and electronic structure of two structurally similar metal–organic networks grown on the Au(111) surface is investigated by scanning tunnelling microscopy (STM) and spectroscopy (STS) combined with density functional theory (DFT) calculations. The networks are composed of (i) F4TCNQ (C12F4N4, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquino–dimethane) molecules and Au adatoms segregated from the pristine metal surface, and (ii) TCNQ (C12H4N4, 7,7,8,8-tetracyanoquinodimethane) and codeposited Mn atoms. In both cases, the strong electron acceptor character of the molecules results in metal–to-ligand charge transfer to the lowest unoccupied molecular orbital (LUMO). The amount of electrons donated from the 4-fold coordinated Mn atoms to TCNQ is higher compared to the 2-fold coordinated Au adatoms to F4TCNQ. This behavior is reflected in the appearance of distinct spectral features in STS data in the energy region close to the Fermi level resulting from the intricate interplay between surface states, adatom states, and molecular orbitals. These observations are consistent with a picture in which the LUMO of the TCNQ acceptor molecule hybridizes with Mn and Au substrate metal states becoming practically filled, while the LUMO of F4TCNQ is only partially filled despite being the stronger electron acceptor. Our results reveal the importance of the type of bonding between the strong acceptor and the metal center (Au or Mn) as well as its coordination in the determination of the charge transfer to the adlayer, which is important for its electronic properties.Fil: Faraggi, Marisa Noemi. Consejo Nacional de Investigaciónes Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Astronomía y Física del Espacio. - Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Astronomía y Física del Espacio; Argentina. Donostia International Physics Center; EspañaFil: Jiang, Nan. Max-planck-institut Fu R Festkorperforschung; AlemaniaFil: Gonzalez Lakuntza, Nora. Donostia International Physics Center; EspañaFil: Langner, Alexander. Max-planck-institut Fu R Festkorperforschung; AlemaniaFil: Stepanow, Sebastian. Max-planck-institut Fu R Festkorperforschung; AlemaniaFil: Kern, Klaus. Max-planck-institut Fur Festkorperforschun; AlemaniaFil: Arnau, Andres. Max-planck-institut Fur Festkorperforschun; AlemaniaAmerican Chemical Society2012-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/19515Faraggi, Marisa Noemi; Jiang, Nan; Gonzalez Lakuntza, Nora; Langner, Alexander; Stepanow, Sebastian; et al.; Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules; American Chemical Society; Journal of Physical Chemistry C; 116; 10-2012; 24558-245651932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp306780ninfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp306780ninfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:01:18Zoai:ri.conicet.gov.ar:11336/19515instacron: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:34982025-09-03 10:01:18.807CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
title Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
spellingShingle Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
Faraggi, Marisa Noemi
Surface
Network
Molecule
Acceptor
title_short Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
title_full Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
title_fullStr Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
title_full_unstemmed Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
title_sort Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
dc.creator.none.fl_str_mv Faraggi, Marisa Noemi
Jiang, Nan
Gonzalez Lakuntza, Nora
Langner, Alexander
Stepanow, Sebastian
Kern, Klaus
Arnau, Andres
author Faraggi, Marisa Noemi
author_facet Faraggi, Marisa Noemi
Jiang, Nan
Gonzalez Lakuntza, Nora
Langner, Alexander
Stepanow, Sebastian
Kern, Klaus
Arnau, Andres
author_role author
author2 Jiang, Nan
Gonzalez Lakuntza, Nora
Langner, Alexander
Stepanow, Sebastian
Kern, Klaus
Arnau, Andres
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Surface
Network
Molecule
Acceptor
topic Surface
Network
Molecule
Acceptor
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The geometric and electronic structure of two structurally similar metal–organic networks grown on the Au(111) surface is investigated by scanning tunnelling microscopy (STM) and spectroscopy (STS) combined with density functional theory (DFT) calculations. The networks are composed of (i) F4TCNQ (C12F4N4, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquino–dimethane) molecules and Au adatoms segregated from the pristine metal surface, and (ii) TCNQ (C12H4N4, 7,7,8,8-tetracyanoquinodimethane) and codeposited Mn atoms. In both cases, the strong electron acceptor character of the molecules results in metal–to-ligand charge transfer to the lowest unoccupied molecular orbital (LUMO). The amount of electrons donated from the 4-fold coordinated Mn atoms to TCNQ is higher compared to the 2-fold coordinated Au adatoms to F4TCNQ. This behavior is reflected in the appearance of distinct spectral features in STS data in the energy region close to the Fermi level resulting from the intricate interplay between surface states, adatom states, and molecular orbitals. These observations are consistent with a picture in which the LUMO of the TCNQ acceptor molecule hybridizes with Mn and Au substrate metal states becoming practically filled, while the LUMO of F4TCNQ is only partially filled despite being the stronger electron acceptor. Our results reveal the importance of the type of bonding between the strong acceptor and the metal center (Au or Mn) as well as its coordination in the determination of the charge transfer to the adlayer, which is important for its electronic properties.
Fil: Faraggi, Marisa Noemi. Consejo Nacional de Investigaciónes Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Astronomía y Física del Espacio. - Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Astronomía y Física del Espacio; Argentina. Donostia International Physics Center; España
Fil: Jiang, Nan. Max-planck-institut Fu R Festkorperforschung; Alemania
Fil: Gonzalez Lakuntza, Nora. Donostia International Physics Center; España
Fil: Langner, Alexander. Max-planck-institut Fu R Festkorperforschung; Alemania
Fil: Stepanow, Sebastian. Max-planck-institut Fu R Festkorperforschung; Alemania
Fil: Kern, Klaus. Max-planck-institut Fur Festkorperforschun; Alemania
Fil: Arnau, Andres. Max-planck-institut Fur Festkorperforschun; Alemania
description The geometric and electronic structure of two structurally similar metal–organic networks grown on the Au(111) surface is investigated by scanning tunnelling microscopy (STM) and spectroscopy (STS) combined with density functional theory (DFT) calculations. The networks are composed of (i) F4TCNQ (C12F4N4, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquino–dimethane) molecules and Au adatoms segregated from the pristine metal surface, and (ii) TCNQ (C12H4N4, 7,7,8,8-tetracyanoquinodimethane) and codeposited Mn atoms. In both cases, the strong electron acceptor character of the molecules results in metal–to-ligand charge transfer to the lowest unoccupied molecular orbital (LUMO). The amount of electrons donated from the 4-fold coordinated Mn atoms to TCNQ is higher compared to the 2-fold coordinated Au adatoms to F4TCNQ. This behavior is reflected in the appearance of distinct spectral features in STS data in the energy region close to the Fermi level resulting from the intricate interplay between surface states, adatom states, and molecular orbitals. These observations are consistent with a picture in which the LUMO of the TCNQ acceptor molecule hybridizes with Mn and Au substrate metal states becoming practically filled, while the LUMO of F4TCNQ is only partially filled despite being the stronger electron acceptor. Our results reveal the importance of the type of bonding between the strong acceptor and the metal center (Au or Mn) as well as its coordination in the determination of the charge transfer to the adlayer, which is important for its electronic properties.
publishDate 2012
dc.date.none.fl_str_mv 2012-10
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/11336/19515
Faraggi, Marisa Noemi; Jiang, Nan; Gonzalez Lakuntza, Nora; Langner, Alexander; Stepanow, Sebastian; et al.; Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules; American Chemical Society; Journal of Physical Chemistry C; 116; 10-2012; 24558-24565
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/19515
identifier_str_mv Faraggi, Marisa Noemi; Jiang, Nan; Gonzalez Lakuntza, Nora; Langner, Alexander; Stepanow, Sebastian; et al.; Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules; American Chemical Society; Journal of Physical Chemistry C; 116; 10-2012; 24558-24565
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jp306780n
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp306780n
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 13.13397

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