Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster

Autores
Alborés, Pablo; Rentschler, Eva
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report the first example of a polynuclear discrete coordination compound exhibiting only bpym bridges and containing a first-row d transition metal. A smooth self-assembly one-pot synthetic route, starting from simply FeCl 2 and FeCl3 hydrates, allowed us to prepare a tetranuclear Fe4 cluster with a stairway-like structure and the formula cis-{[(H2O)Cl3FeIII-μ(bpym)Fe IICl2]}2-μ(bpym) (1). All spectroscopic data suggest that complex 1 is a valence-localized mixed-valent Fe II-FeIII cluster with typical Mössbauer lines for both sites, which do not change with temperature. Reflectance spectroscopy did not allow one to distinguish an intervalence charge-transfer band. However, time-dependent density functional theory (DFT) calculations predict a weak high-energy FeII → FeIII transition. Regarding the magnetic properties, the high-spin FeII and FeIII ions interact in a weakly antiferromagnetic way with isotropic J constants of only a few wavenumbers as derived from direct-current susceptibility and magnetization data. Broken-symmetry DFT calculations support these observations. © 2010 American Chemical Society.
Fil: Alborés, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Johannes Gutenberg Universitat Mainz; Alemania
Fil: Rentschler, Eva. Johannes Gutenberg Universitat Mainz; Alemania
Materia
Bipyrimidine Bridge
Tetranuclear
Mixed Valent
Iron
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:11336/72006
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/72006
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} clusterAlborés, PabloRentschler, EvaBipyrimidine BridgeTetranuclearMixed ValentIronhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report the first example of a polynuclear discrete coordination compound exhibiting only bpym bridges and containing a first-row d transition metal. A smooth self-assembly one-pot synthetic route, starting from simply FeCl 2 and FeCl3 hydrates, allowed us to prepare a tetranuclear Fe4 cluster with a stairway-like structure and the formula cis-{[(H2O)Cl3FeIII-μ(bpym)Fe IICl2]}2-μ(bpym) (1). All spectroscopic data suggest that complex 1 is a valence-localized mixed-valent Fe II-FeIII cluster with typical Mössbauer lines for both sites, which do not change with temperature. Reflectance spectroscopy did not allow one to distinguish an intervalence charge-transfer band. However, time-dependent density functional theory (DFT) calculations predict a weak high-energy FeII → FeIII transition. Regarding the magnetic properties, the high-spin FeII and FeIII ions interact in a weakly antiferromagnetic way with isotropic J constants of only a few wavenumbers as derived from direct-current susceptibility and magnetization data. Broken-symmetry DFT calculations support these observations. © 2010 American Chemical Society.Fil: Alborés, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Johannes Gutenberg Universitat Mainz; AlemaniaFil: Rentschler, Eva. Johannes Gutenberg Universitat Mainz; AlemaniaAmerican Chemical Society2010-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/72006Alborés, Pablo; Rentschler, Eva; Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster; American Chemical Society; Inorganic Chemistry; 49; 19; 10-2010; 8953-89610020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic1013472info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/ic1013472info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:29:15Zoai:ri.conicet.gov.ar:11336/72006instacron: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 10:29:15.461CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster
title Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster
spellingShingle Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster
Alborés, Pablo
Bipyrimidine Bridge
Tetranuclear
Mixed Valent
Iron
title_short Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster
title_full Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster
title_fullStr Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster
title_full_unstemmed Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster
title_sort Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster
dc.creator.none.fl_str_mv Alborés, Pablo
Rentschler, Eva
author Alborés, Pablo
author_facet Alborés, Pablo
Rentschler, Eva
author_role author
author2 Rentschler, Eva
author2_role author
dc.subject.none.fl_str_mv Bipyrimidine Bridge
Tetranuclear
Mixed Valent
Iron
topic Bipyrimidine Bridge
Tetranuclear
Mixed Valent
Iron
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 report the first example of a polynuclear discrete coordination compound exhibiting only bpym bridges and containing a first-row d transition metal. A smooth self-assembly one-pot synthetic route, starting from simply FeCl 2 and FeCl3 hydrates, allowed us to prepare a tetranuclear Fe4 cluster with a stairway-like structure and the formula cis-{[(H2O)Cl3FeIII-μ(bpym)Fe IICl2]}2-μ(bpym) (1). All spectroscopic data suggest that complex 1 is a valence-localized mixed-valent Fe II-FeIII cluster with typical Mössbauer lines for both sites, which do not change with temperature. Reflectance spectroscopy did not allow one to distinguish an intervalence charge-transfer band. However, time-dependent density functional theory (DFT) calculations predict a weak high-energy FeII → FeIII transition. Regarding the magnetic properties, the high-spin FeII and FeIII ions interact in a weakly antiferromagnetic way with isotropic J constants of only a few wavenumbers as derived from direct-current susceptibility and magnetization data. Broken-symmetry DFT calculations support these observations. © 2010 American Chemical Society.
Fil: Alborés, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Johannes Gutenberg Universitat Mainz; Alemania
Fil: Rentschler, Eva. Johannes Gutenberg Universitat Mainz; Alemania
description We report the first example of a polynuclear discrete coordination compound exhibiting only bpym bridges and containing a first-row d transition metal. A smooth self-assembly one-pot synthetic route, starting from simply FeCl 2 and FeCl3 hydrates, allowed us to prepare a tetranuclear Fe4 cluster with a stairway-like structure and the formula cis-{[(H2O)Cl3FeIII-μ(bpym)Fe IICl2]}2-μ(bpym) (1). All spectroscopic data suggest that complex 1 is a valence-localized mixed-valent Fe II-FeIII cluster with typical Mössbauer lines for both sites, which do not change with temperature. Reflectance spectroscopy did not allow one to distinguish an intervalence charge-transfer band. However, time-dependent density functional theory (DFT) calculations predict a weak high-energy FeII → FeIII transition. Regarding the magnetic properties, the high-spin FeII and FeIII ions interact in a weakly antiferromagnetic way with isotropic J constants of only a few wavenumbers as derived from direct-current susceptibility and magnetization data. Broken-symmetry DFT calculations support these observations. © 2010 American Chemical Society.
publishDate 2010
dc.date.none.fl_str_mv 2010-10
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/11336/72006
Alborés, Pablo; Rentschler, Eva; Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster; American Chemical Society; Inorganic Chemistry; 49; 19; 10-2010; 8953-8961
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/72006
identifier_str_mv Alborés, Pablo; Rentschler, Eva; Cis -2,2′-bipyrimidine-bridged polynuclear complex: A stairway-like mixed-valent {Fe4} cluster; American Chemical Society; Inorganic Chemistry; 49; 19; 10-2010; 8953-8961
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/doi/10.1021/ic1013472
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/ic1013472
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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