Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling

Autores
Pérez, Ana Laura; Neuman, Nicolás Ignacio; Baggio, Ricardo Fortunato; Ramos, Carlos Alberto; Dalosto, Sergio Daniel; Rizzi, Alberto Claudio; Brondino, Carlos Dante
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report EPR and magnetic measurements of diaqua-(pyridine-2,6-dicarboxylato)Copper(II) together with computational calculations. This compound consists of an extended lattice of magnetically equivalent copper(II) ions in which the copper centers are linked by hydrophobic interactions such as π–π, π–metal, and Y–X…π, and hydrogen bonds involving different topologies, viz., [sbnd]Cu[sbnd]Oeq…Oeq[sbnd]Cu[sbnd], [sbnd]Cu[sbnd]Oeq…Oap[sbnd]Cu[sbnd], and [sbnd]Cu[sbnd]Oeq…O[dbnd]C[sbnd]Oeq[sbnd]Cu[sbnd]. The powder EPR spectrum shows nearly axial symmetry with non-resolved hyperfine structure with the copper nucleus, suggesting the presence of intercenter isotropic exchange interactions. Single crystal EPR experiments show a single lorentzian resonance line for all the magnetic field orientations investigated, typical of an extended exchange coupled system. Susceptibility measurements showed weakly antiferromagnetically coupled Cu(II) ions (J = −0.79 (4) cm−1). Using Anderson's exchange narrowing model for the collapse of the hyperfine structure, EPR yielded |J| = 0.6 (1) cm−1. The distinct contributions of the different chemical pathways to the experimentally determined J-value are analyzed through first principle computational calculations.
Fil: Pérez, Ana Laura. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Ramos, Carlos Alberto. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Dalosto, Sergio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina
Fil: Rizzi, Alberto Claudio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Materia
Computational Calculation
Copper Complex
Epr
Noncovalent Interaction
Superexchange
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:11336/58686
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/58686
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic couplingPérez, Ana LauraNeuman, Nicolás IgnacioBaggio, Ricardo FortunatoRamos, Carlos AlbertoDalosto, Sergio DanielRizzi, Alberto ClaudioBrondino, Carlos DanteComputational CalculationCopper ComplexEprNoncovalent InteractionSuperexchangehttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We report EPR and magnetic measurements of diaqua-(pyridine-2,6-dicarboxylato)Copper(II) together with computational calculations. This compound consists of an extended lattice of magnetically equivalent copper(II) ions in which the copper centers are linked by hydrophobic interactions such as π–π, π–metal, and Y–X…π, and hydrogen bonds involving different topologies, viz., [sbnd]Cu[sbnd]Oeq…Oeq[sbnd]Cu[sbnd], [sbnd]Cu[sbnd]Oeq…Oap[sbnd]Cu[sbnd], and [sbnd]Cu[sbnd]Oeq…O[dbnd]C[sbnd]Oeq[sbnd]Cu[sbnd]. The powder EPR spectrum shows nearly axial symmetry with non-resolved hyperfine structure with the copper nucleus, suggesting the presence of intercenter isotropic exchange interactions. Single crystal EPR experiments show a single lorentzian resonance line for all the magnetic field orientations investigated, typical of an extended exchange coupled system. Susceptibility measurements showed weakly antiferromagnetically coupled Cu(II) ions (J = −0.79 (4) cm−1). Using Anderson's exchange narrowing model for the collapse of the hyperfine structure, EPR yielded |J| = 0.6 (1) cm−1. The distinct contributions of the different chemical pathways to the experimentally determined J-value are analyzed through first principle computational calculations.Fil: Pérez, Ana Laura. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaFil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: Ramos, Carlos Alberto. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaFil: Dalosto, Sergio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; ArgentinaFil: Rizzi, Alberto Claudio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaFil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaPergamon-Elsevier Science Ltd2017-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/58686Pérez, Ana Laura; Neuman, Nicolás Ignacio; Baggio, Ricardo Fortunato; Ramos, Carlos Alberto; Dalosto, Sergio Daniel; et al.; Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling; Pergamon-Elsevier Science Ltd; Polyhedron; 123; 2-2017; 404-4100277-5387CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.poly.2016.12.018info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0277538716306696info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:35:25Zoai:ri.conicet.gov.ar:11336/58686instacron: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:34982025-11-12 09:35:25.705CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling
title Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling
spellingShingle Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling
Pérez, Ana Laura
Computational Calculation
Copper Complex
Epr
Noncovalent Interaction
Superexchange
title_short Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling
title_full Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling
title_fullStr Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling
title_full_unstemmed Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling
title_sort Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling
dc.creator.none.fl_str_mv Pérez, Ana Laura
Neuman, Nicolás Ignacio
Baggio, Ricardo Fortunato
Ramos, Carlos Alberto
Dalosto, Sergio Daniel
Rizzi, Alberto Claudio
Brondino, Carlos Dante
author Pérez, Ana Laura
author_facet Pérez, Ana Laura
Neuman, Nicolás Ignacio
Baggio, Ricardo Fortunato
Ramos, Carlos Alberto
Dalosto, Sergio Daniel
Rizzi, Alberto Claudio
Brondino, Carlos Dante
author_role author
author2 Neuman, Nicolás Ignacio
Baggio, Ricardo Fortunato
Ramos, Carlos Alberto
Dalosto, Sergio Daniel
Rizzi, Alberto Claudio
Brondino, Carlos Dante
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Computational Calculation
Copper Complex
Epr
Noncovalent Interaction
Superexchange
topic Computational Calculation
Copper Complex
Epr
Noncovalent Interaction
Superexchange
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report EPR and magnetic measurements of diaqua-(pyridine-2,6-dicarboxylato)Copper(II) together with computational calculations. This compound consists of an extended lattice of magnetically equivalent copper(II) ions in which the copper centers are linked by hydrophobic interactions such as π–π, π–metal, and Y–X…π, and hydrogen bonds involving different topologies, viz., [sbnd]Cu[sbnd]Oeq…Oeq[sbnd]Cu[sbnd], [sbnd]Cu[sbnd]Oeq…Oap[sbnd]Cu[sbnd], and [sbnd]Cu[sbnd]Oeq…O[dbnd]C[sbnd]Oeq[sbnd]Cu[sbnd]. The powder EPR spectrum shows nearly axial symmetry with non-resolved hyperfine structure with the copper nucleus, suggesting the presence of intercenter isotropic exchange interactions. Single crystal EPR experiments show a single lorentzian resonance line for all the magnetic field orientations investigated, typical of an extended exchange coupled system. Susceptibility measurements showed weakly antiferromagnetically coupled Cu(II) ions (J = −0.79 (4) cm−1). Using Anderson's exchange narrowing model for the collapse of the hyperfine structure, EPR yielded |J| = 0.6 (1) cm−1. The distinct contributions of the different chemical pathways to the experimentally determined J-value are analyzed through first principle computational calculations.
Fil: Pérez, Ana Laura. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Ramos, Carlos Alberto. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Dalosto, Sergio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina
Fil: Rizzi, Alberto Claudio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
description We report EPR and magnetic measurements of diaqua-(pyridine-2,6-dicarboxylato)Copper(II) together with computational calculations. This compound consists of an extended lattice of magnetically equivalent copper(II) ions in which the copper centers are linked by hydrophobic interactions such as π–π, π–metal, and Y–X…π, and hydrogen bonds involving different topologies, viz., [sbnd]Cu[sbnd]Oeq…Oeq[sbnd]Cu[sbnd], [sbnd]Cu[sbnd]Oeq…Oap[sbnd]Cu[sbnd], and [sbnd]Cu[sbnd]Oeq…O[dbnd]C[sbnd]Oeq[sbnd]Cu[sbnd]. The powder EPR spectrum shows nearly axial symmetry with non-resolved hyperfine structure with the copper nucleus, suggesting the presence of intercenter isotropic exchange interactions. Single crystal EPR experiments show a single lorentzian resonance line for all the magnetic field orientations investigated, typical of an extended exchange coupled system. Susceptibility measurements showed weakly antiferromagnetically coupled Cu(II) ions (J = −0.79 (4) cm−1). Using Anderson's exchange narrowing model for the collapse of the hyperfine structure, EPR yielded |J| = 0.6 (1) cm−1. The distinct contributions of the different chemical pathways to the experimentally determined J-value are analyzed through first principle computational calculations.
publishDate 2017
dc.date.none.fl_str_mv 2017-02
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/11336/58686
Pérez, Ana Laura; Neuman, Nicolás Ignacio; Baggio, Ricardo Fortunato; Ramos, Carlos Alberto; Dalosto, Sergio Daniel; et al.; Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling; Pergamon-Elsevier Science Ltd; Polyhedron; 123; 2-2017; 404-410
0277-5387
CONICET Digital
CONICET
url http://hdl.handle.net/11336/58686
identifier_str_mv Pérez, Ana Laura; Neuman, Nicolás Ignacio; Baggio, Ricardo Fortunato; Ramos, Carlos Alberto; Dalosto, Sergio Daniel; et al.; Exchange interaction between S = 1/2 centers bridged by multiple noncovalent interactions: Contribution of the individual chemical pathways to the magnetic coupling; Pergamon-Elsevier Science Ltd; Polyhedron; 123; 2-2017; 404-410
0277-5387
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.poly.2016.12.018
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0277538716306696
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 Pergamon-Elsevier Science Ltd
publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
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
_version_ 1848597190499368960
score 13.24909

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