Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates

Autores
Castro, Maria Ana; Roitberg, Esteban Gabriel; Cukiernik, Fabio Daniel
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Computational methods (DFT at the B3LYP, PBE0 and m06 levels, MO fragments decomposition, and the broken symmetry approach) have been used to evaluate the influence of the bridging ligand (BL) on the extent of electron delocalization in coordination polymers based on diruthenium tetracarboxylates. The efficiency of three different nitrogenated axial ligands, namely pyrazine (pz), phenazine (phz), and tetrazine (tz), to mediate electron coupling between Ru2(II,II) or Ru2(II,III) centers has been estimated through four different parameters: calculated Ru-N distances, HOMO-LUMO gaps, HOMO and LUMO compositions, and magnetic coupling constants J. All these parameters pointed toward a coordination polymer based on Ru2(II,II) centers axially linked by tetrazine being the best candidate for exhibiting electron delocalization through the Ru2−BL framework. Such a compound has been synthesized and characterized; its vis-NIR spectrum exhibited the predicted features, mainly an intense low-energy MLCT band, assigned to the expected Ru2(II,II) - tz process associated with electron delocalization.
Fil: Castro, Maria Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de Los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
Fil: Roitberg, Esteban Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Astronomía y Física del Espacio(i); Argentina. University Of Florida; Estados Unidos
Fil: Cukiernik, Fabio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de Los Materiales, Medioambiente y Energía; Argentina. University Of Florida; Estados Unidos
Materia
Coordination Polymers
Electronic Delocalization
Diruthenium Carboxylates
Tetrazine
Broken Symmetry
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:11336/7802
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Electronic Delocalization in Coordination Polymers Based on Bimetallic CarboxylatesCastro, Maria AnaRoitberg, Esteban GabrielCukiernik, Fabio DanielCoordination PolymersElectronic DelocalizationDiruthenium CarboxylatesTetrazineBroken Symmetryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Computational methods (DFT at the B3LYP, PBE0 and m06 levels, MO fragments decomposition, and the broken symmetry approach) have been used to evaluate the influence of the bridging ligand (BL) on the extent of electron delocalization in coordination polymers based on diruthenium tetracarboxylates. The efficiency of three different nitrogenated axial ligands, namely pyrazine (pz), phenazine (phz), and tetrazine (tz), to mediate electron coupling between Ru2(II,II) or Ru2(II,III) centers has been estimated through four different parameters: calculated Ru-N distances, HOMO-LUMO gaps, HOMO and LUMO compositions, and magnetic coupling constants J. All these parameters pointed toward a coordination polymer based on Ru2(II,II) centers axially linked by tetrazine being the best candidate for exhibiting electron delocalization through the Ru2−BL framework. Such a compound has been synthesized and characterized; its vis-NIR spectrum exhibited the predicted features, mainly an intense low-energy MLCT band, assigned to the expected Ru2(II,II) - tz process associated with electron delocalization.Fil: Castro, Maria Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de Los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; ArgentinaFil: Roitberg, Esteban Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Astronomía y Física del Espacio(i); Argentina. University Of Florida; Estados UnidosFil: Cukiernik, Fabio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de Los Materiales, Medioambiente y Energía; Argentina. University Of Florida; Estados UnidosAmerican Chemical Society2013-04-29info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/7802Castro, Maria Ana; Roitberg, Esteban Gabriel; Cukiernik, Fabio Daniel; Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates; American Chemical Society; Journal of Chemical Theory and Computation; 9; 6; 29-4-2013; 2609-26161549-9626enginfo:eu-repo/semantics/altIdentifier/url/http://dx.doi.org/10.1021/ct400179tinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ct400179tinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:57:37Zoai:ri.conicet.gov.ar:11336/7802instacron: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 09:57:37.239CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates
title Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates
spellingShingle Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates
Castro, Maria Ana
Coordination Polymers
Electronic Delocalization
Diruthenium Carboxylates
Tetrazine
Broken Symmetry
title_short Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates
title_full Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates
title_fullStr Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates
title_full_unstemmed Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates
title_sort Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates
dc.creator.none.fl_str_mv Castro, Maria Ana
Roitberg, Esteban Gabriel
Cukiernik, Fabio Daniel
author Castro, Maria Ana
author_facet Castro, Maria Ana
Roitberg, Esteban Gabriel
Cukiernik, Fabio Daniel
author_role author
author2 Roitberg, Esteban Gabriel
Cukiernik, Fabio Daniel
author2_role author
author
dc.subject.none.fl_str_mv Coordination Polymers
Electronic Delocalization
Diruthenium Carboxylates
Tetrazine
Broken Symmetry
topic Coordination Polymers
Electronic Delocalization
Diruthenium Carboxylates
Tetrazine
Broken Symmetry
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Computational methods (DFT at the B3LYP, PBE0 and m06 levels, MO fragments decomposition, and the broken symmetry approach) have been used to evaluate the influence of the bridging ligand (BL) on the extent of electron delocalization in coordination polymers based on diruthenium tetracarboxylates. The efficiency of three different nitrogenated axial ligands, namely pyrazine (pz), phenazine (phz), and tetrazine (tz), to mediate electron coupling between Ru2(II,II) or Ru2(II,III) centers has been estimated through four different parameters: calculated Ru-N distances, HOMO-LUMO gaps, HOMO and LUMO compositions, and magnetic coupling constants J. All these parameters pointed toward a coordination polymer based on Ru2(II,II) centers axially linked by tetrazine being the best candidate for exhibiting electron delocalization through the Ru2−BL framework. Such a compound has been synthesized and characterized; its vis-NIR spectrum exhibited the predicted features, mainly an intense low-energy MLCT band, assigned to the expected Ru2(II,II) - tz process associated with electron delocalization.
Fil: Castro, Maria Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de Los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
Fil: Roitberg, Esteban Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Astronomía y Física del Espacio(i); Argentina. University Of Florida; Estados Unidos
Fil: Cukiernik, Fabio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de Los Materiales, Medioambiente y Energía; Argentina. University Of Florida; Estados Unidos
description Computational methods (DFT at the B3LYP, PBE0 and m06 levels, MO fragments decomposition, and the broken symmetry approach) have been used to evaluate the influence of the bridging ligand (BL) on the extent of electron delocalization in coordination polymers based on diruthenium tetracarboxylates. The efficiency of three different nitrogenated axial ligands, namely pyrazine (pz), phenazine (phz), and tetrazine (tz), to mediate electron coupling between Ru2(II,II) or Ru2(II,III) centers has been estimated through four different parameters: calculated Ru-N distances, HOMO-LUMO gaps, HOMO and LUMO compositions, and magnetic coupling constants J. All these parameters pointed toward a coordination polymer based on Ru2(II,II) centers axially linked by tetrazine being the best candidate for exhibiting electron delocalization through the Ru2−BL framework. Such a compound has been synthesized and characterized; its vis-NIR spectrum exhibited the predicted features, mainly an intense low-energy MLCT band, assigned to the expected Ru2(II,II) - tz process associated with electron delocalization.
publishDate 2013
dc.date.none.fl_str_mv 2013-04-29
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/11336/7802
Castro, Maria Ana; Roitberg, Esteban Gabriel; Cukiernik, Fabio Daniel; Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates; American Chemical Society; Journal of Chemical Theory and Computation; 9; 6; 29-4-2013; 2609-2616
1549-9626
url http://hdl.handle.net/11336/7802
identifier_str_mv Castro, Maria Ana; Roitberg, Esteban Gabriel; Cukiernik, Fabio Daniel; Electronic Delocalization in Coordination Polymers Based on Bimetallic Carboxylates; American Chemical Society; Journal of Chemical Theory and Computation; 9; 6; 29-4-2013; 2609-2616
1549-9626
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://dx.doi.org/10.1021/ct400179t
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ct400179t
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
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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