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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/111274
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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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1844613393355374592 |
score |
13.070432 |