Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units

Autores
Sartoris, Rosana Patricia; Santana, Vinicius T.; Freire Espeleta, Eleonora; Baggio, Ricardo Fortunato; Nascimento, Otaciro R.; Calvo, Rafael
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
To investigate the magnetic properties and the spin entanglement of dinuclear arrays, we prepared compounds [{Cu(pAB)(phen)H2O}2·NO3·pABH·2H2O], 1, and [Cu2(pAB)2(phen)2pz]n, 2 (pABH = p-aminobenzoic acid, phen = 1,10-phenanthroline and pz = pyrazine). The structure of 1 is known and we report here that of 2. They contain similar dinuclear units of CuII ions with 1/2-spins S1 and S2 bridged by pairs of pABmolecules, with similar intradinuclear exchange Hex ¼ J0S1 S2 and fine interactions HD ¼ S1 ð2DÞ S2, but different 3D crystal arrays with weak interdinuclear exchange J?, stronger in 2 than in 1. To investigate the magnetic properties and the spin entanglement produced by J?, we collected the powder spectra of 1 and 2 at 9.4 GHz and T between 5 and 298 K, and at 34.4 GHz and T = 298 K and single-crystal spectra at room T and 34.4 GHz as a function of magnetic field (B0) orientation in three crystal planes, calculating intradinuclear magnetic parameters J0 = (−75 ± 1) cm−1, J0 = (−78 ± 2) cm−1, |D(1)| = (0.142 ± 0.006)cm−1, |D(2)| = (0.141 ± 0.006) cm−1 and E(1) ∼ E(2) ∼ 0. Single crystal data indicate a quantum entangled phase in 2 around the crossing between two fine structure EPR absorption peaks within the spin triplet. This phase also shows up in powder samples of 2 as a U-peak collecting the signals of the entangled microcrystals, a feature that allows estimating |J?|. Transitions between the two quantum phases are observed in single crystals of 2 changing the orientation of B0. We estimate interdinuclear exchange couplings |J?(1)| < 0.003 cm−1 and |J?(2)| = (0.013 ± 0.005) cm−1, in 1 and 2, respectively. Our analysis indicates that the standard approximation of a spin Hamiltonian with S = 1 for the dinuclear spectra is valid only when the interdinuclear coupling is large enough, as for compound 2 (|J?(2)/J0 | ∼ 1.7 × 10−4). When J? is negligible as in 1, the real spin Hamiltonian with two spins 1/2 has to be used. Broken-symmetry DFT predicts correctly the nature and magnitude of the antiferromagnetic exchange coupling in 1 and 2 and ferromagnetic interdinuclear coupling for compound 2.
Fil: Sartoris, Rosana Patricia. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Santana, Vinicius T.. Central European Institute Of Technology; República Checa
Fil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; Argentina
Fil: Nascimento, Otaciro R.. Universidad de Sao Paulo; Brasil
Fil: Calvo, Rafael. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. 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
Materia
MAGNETISM
DIMERIC COMPOUND
ENTANGLEMENT
EPR
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
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oai:ri.conicet.gov.ar:11336/111274

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oai_identifier_str oai:ri.conicet.gov.ar:11336/111274
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear unitsSartoris, Rosana PatriciaSantana, Vinicius T.Freire Espeleta, EleonoraBaggio, Ricardo FortunatoNascimento, Otaciro R.Calvo, RafaelMAGNETISMDIMERIC COMPOUNDENTANGLEMENTEPRhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1To investigate the magnetic properties and the spin entanglement of dinuclear arrays, we prepared compounds [{Cu(pAB)(phen)H2O}2·NO3·pABH·2H2O], 1, and [Cu2(pAB)2(phen)2pz]n, 2 (pABH = p-aminobenzoic acid, phen = 1,10-phenanthroline and pz = pyrazine). The structure of 1 is known and we report here that of 2. They contain similar dinuclear units of CuII ions with 1/2-spins S1 and S2 bridged by pairs of pABmolecules, with similar intradinuclear exchange Hex ¼ J0S1 S2 and fine interactions HD ¼ S1 ð2DÞ S2, but different 3D crystal arrays with weak interdinuclear exchange J?, stronger in 2 than in 1. To investigate the magnetic properties and the spin entanglement produced by J?, we collected the powder spectra of 1 and 2 at 9.4 GHz and T between 5 and 298 K, and at 34.4 GHz and T = 298 K and single-crystal spectra at room T and 34.4 GHz as a function of magnetic field (B0) orientation in three crystal planes, calculating intradinuclear magnetic parameters J0 = (−75 ± 1) cm−1, J0 = (−78 ± 2) cm−1, |D(1)| = (0.142 ± 0.006)cm−1, |D(2)| = (0.141 ± 0.006) cm−1 and E(1) ∼ E(2) ∼ 0. Single crystal data indicate a quantum entangled phase in 2 around the crossing between two fine structure EPR absorption peaks within the spin triplet. This phase also shows up in powder samples of 2 as a U-peak collecting the signals of the entangled microcrystals, a feature that allows estimating |J?|. Transitions between the two quantum phases are observed in single crystals of 2 changing the orientation of B0. We estimate interdinuclear exchange couplings |J?(1)| < 0.003 cm−1 and |J?(2)| = (0.013 ± 0.005) cm−1, in 1 and 2, respectively. Our analysis indicates that the standard approximation of a spin Hamiltonian with S = 1 for the dinuclear spectra is valid only when the interdinuclear coupling is large enough, as for compound 2 (|J?(2)/J0 | ∼ 1.7 × 10−4). When J? is negligible as in 1, the real spin Hamiltonian with two spins 1/2 has to be used. Broken-symmetry DFT predicts correctly the nature and magnitude of the antiferromagnetic exchange coupling in 1 and 2 and ferromagnetic interdinuclear coupling for compound 2.Fil: Sartoris, Rosana Patricia. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaFil: Santana, Vinicius T.. Central European Institute Of Technology; República ChecaFil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; ArgentinaFil: Nascimento, Otaciro R.. Universidad de Sao Paulo; BrasilFil: Calvo, Rafael. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. 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; ArgentinaRoyal Society of Chemistry2020-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/111274Sartoris, Rosana Patricia; Santana, Vinicius T.; Freire Espeleta, Eleonora; Baggio, Ricardo Fortunato; Nascimento, Otaciro R.; et al.; Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units; Royal Society of Chemistry; Dalton Transactions; 49; 16; 6-2020; 5228-52401477-9226CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://xlink.rsc.org/?DOI=D0DT00567Cinfo:eu-repo/semantics/altIdentifier/doi/10.1039/D0DT00567Cinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:44:15Zoai:ri.conicet.gov.ar:11336/111274instacron: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 09:44:15.563CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units
title Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units
spellingShingle Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units
Sartoris, Rosana Patricia
MAGNETISM
DIMERIC COMPOUND
ENTANGLEMENT
EPR
title_short Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units
title_full Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units
title_fullStr Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units
title_full_unstemmed Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units
title_sort Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units
dc.creator.none.fl_str_mv Sartoris, Rosana Patricia
Santana, Vinicius T.
Freire Espeleta, Eleonora
Baggio, Ricardo Fortunato
Nascimento, Otaciro R.
Calvo, Rafael
author Sartoris, Rosana Patricia
author_facet Sartoris, Rosana Patricia
Santana, Vinicius T.
Freire Espeleta, Eleonora
Baggio, Ricardo Fortunato
Nascimento, Otaciro R.
Calvo, Rafael
author_role author
author2 Santana, Vinicius T.
Freire Espeleta, Eleonora
Baggio, Ricardo Fortunato
Nascimento, Otaciro R.
Calvo, Rafael
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv MAGNETISM
DIMERIC COMPOUND
ENTANGLEMENT
EPR
topic MAGNETISM
DIMERIC COMPOUND
ENTANGLEMENT
EPR
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv To investigate the magnetic properties and the spin entanglement of dinuclear arrays, we prepared compounds [{Cu(pAB)(phen)H2O}2·NO3·pABH·2H2O], 1, and [Cu2(pAB)2(phen)2pz]n, 2 (pABH = p-aminobenzoic acid, phen = 1,10-phenanthroline and pz = pyrazine). The structure of 1 is known and we report here that of 2. They contain similar dinuclear units of CuII ions with 1/2-spins S1 and S2 bridged by pairs of pABmolecules, with similar intradinuclear exchange Hex ¼ J0S1 S2 and fine interactions HD ¼ S1 ð2DÞ S2, but different 3D crystal arrays with weak interdinuclear exchange J?, stronger in 2 than in 1. To investigate the magnetic properties and the spin entanglement produced by J?, we collected the powder spectra of 1 and 2 at 9.4 GHz and T between 5 and 298 K, and at 34.4 GHz and T = 298 K and single-crystal spectra at room T and 34.4 GHz as a function of magnetic field (B0) orientation in three crystal planes, calculating intradinuclear magnetic parameters J0 = (−75 ± 1) cm−1, J0 = (−78 ± 2) cm−1, |D(1)| = (0.142 ± 0.006)cm−1, |D(2)| = (0.141 ± 0.006) cm−1 and E(1) ∼ E(2) ∼ 0. Single crystal data indicate a quantum entangled phase in 2 around the crossing between two fine structure EPR absorption peaks within the spin triplet. This phase also shows up in powder samples of 2 as a U-peak collecting the signals of the entangled microcrystals, a feature that allows estimating |J?|. Transitions between the two quantum phases are observed in single crystals of 2 changing the orientation of B0. We estimate interdinuclear exchange couplings |J?(1)| < 0.003 cm−1 and |J?(2)| = (0.013 ± 0.005) cm−1, in 1 and 2, respectively. Our analysis indicates that the standard approximation of a spin Hamiltonian with S = 1 for the dinuclear spectra is valid only when the interdinuclear coupling is large enough, as for compound 2 (|J?(2)/J0 | ∼ 1.7 × 10−4). When J? is negligible as in 1, the real spin Hamiltonian with two spins 1/2 has to be used. Broken-symmetry DFT predicts correctly the nature and magnitude of the antiferromagnetic exchange coupling in 1 and 2 and ferromagnetic interdinuclear coupling for compound 2.
Fil: Sartoris, Rosana Patricia. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Santana, Vinicius T.. Central European Institute Of Technology; República Checa
Fil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; Argentina
Fil: Nascimento, Otaciro R.. Universidad de Sao Paulo; Brasil
Fil: Calvo, Rafael. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. 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
description To investigate the magnetic properties and the spin entanglement of dinuclear arrays, we prepared compounds [{Cu(pAB)(phen)H2O}2·NO3·pABH·2H2O], 1, and [Cu2(pAB)2(phen)2pz]n, 2 (pABH = p-aminobenzoic acid, phen = 1,10-phenanthroline and pz = pyrazine). The structure of 1 is known and we report here that of 2. They contain similar dinuclear units of CuII ions with 1/2-spins S1 and S2 bridged by pairs of pABmolecules, with similar intradinuclear exchange Hex ¼ J0S1 S2 and fine interactions HD ¼ S1 ð2DÞ S2, but different 3D crystal arrays with weak interdinuclear exchange J?, stronger in 2 than in 1. To investigate the magnetic properties and the spin entanglement produced by J?, we collected the powder spectra of 1 and 2 at 9.4 GHz and T between 5 and 298 K, and at 34.4 GHz and T = 298 K and single-crystal spectra at room T and 34.4 GHz as a function of magnetic field (B0) orientation in three crystal planes, calculating intradinuclear magnetic parameters J0 = (−75 ± 1) cm−1, J0 = (−78 ± 2) cm−1, |D(1)| = (0.142 ± 0.006)cm−1, |D(2)| = (0.141 ± 0.006) cm−1 and E(1) ∼ E(2) ∼ 0. Single crystal data indicate a quantum entangled phase in 2 around the crossing between two fine structure EPR absorption peaks within the spin triplet. This phase also shows up in powder samples of 2 as a U-peak collecting the signals of the entangled microcrystals, a feature that allows estimating |J?|. Transitions between the two quantum phases are observed in single crystals of 2 changing the orientation of B0. We estimate interdinuclear exchange couplings |J?(1)| < 0.003 cm−1 and |J?(2)| = (0.013 ± 0.005) cm−1, in 1 and 2, respectively. Our analysis indicates that the standard approximation of a spin Hamiltonian with S = 1 for the dinuclear spectra is valid only when the interdinuclear coupling is large enough, as for compound 2 (|J?(2)/J0 | ∼ 1.7 × 10−4). When J? is negligible as in 1, the real spin Hamiltonian with two spins 1/2 has to be used. Broken-symmetry DFT predicts correctly the nature and magnitude of the antiferromagnetic exchange coupling in 1 and 2 and ferromagnetic interdinuclear coupling for compound 2.
publishDate 2020
dc.date.none.fl_str_mv 2020-06
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/11336/111274
Sartoris, Rosana Patricia; Santana, Vinicius T.; Freire Espeleta, Eleonora; Baggio, Ricardo Fortunato; Nascimento, Otaciro R.; et al.; Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units; Royal Society of Chemistry; Dalton Transactions; 49; 16; 6-2020; 5228-5240
1477-9226
CONICET Digital
CONICET
url http://hdl.handle.net/11336/111274
identifier_str_mv Sartoris, Rosana Patricia; Santana, Vinicius T.; Freire Espeleta, Eleonora; Baggio, Ricardo Fortunato; Nascimento, Otaciro R.; et al.; Exchange couplings and quantum phases in two dissimilar arrays of similar copper dinuclear units; Royal Society of Chemistry; Dalton Transactions; 49; 16; 6-2020; 5228-5240
1477-9226
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://xlink.rsc.org/?DOI=D0DT00567C
info:eu-repo/semantics/altIdentifier/doi/10.1039/D0DT00567C
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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