Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>

A complete first-principles bottom-up computational study of the magnetic properties of [Cu(pz)2](ClO4)2 is presented. A remarkable agreement is observed in the whole range of temperatures between simulated and experimental magnetic susceptibility data. Interestingly, the simulated heat capacity val...

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Autores: Vela Llausí, Sergi, Jornet Somoza, Joaquim, Turnbull, Mark M., Feyerherm, Ralf, Novoa Vide, Juan J., Deumal i Solé, Mercè
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2013
País:España
Recursos:Universidad de Barcelona
Repositório:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/208012
Acesso em linha:https://hdl.handle.net/2445/208012
Access Level:Acceso aberto
Palavra-chave:Propietats magnètiques
Lligands
Magnetisme
Magnetic properties
Ligands
Magnetism
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spelling Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>Vela Llausí, SergiJornet Somoza, JoaquimTurnbull, Mark M.Feyerherm, RalfNovoa Vide, Juan J.Deumal i Solé, MercèPropietats magnètiquesLligandsMagnetismeMagnetic propertiesLigandsMagnetismA complete first-principles bottom-up computational study of the magnetic properties of [Cu(pz)2](ClO4)2 is presented. A remarkable agreement is observed in the whole range of temperatures between simulated and experimental magnetic susceptibility data. Interestingly, the simulated heat capacity values show an anomaly close to the Néel temperature of 4.21 K associated with a transition from a two-dimensional (2D) antiferromagnet to a three-dimensional (3D) ordered state. The antiferromagnetic behavior of [Cu(pz)2](ClO4)2 is due to a 2D magnetic topology owing to two antiferromagnetic JAB interactions through pyrazine ligands. Although presenting a very similar molecular arrangement, the numerical values of the two magnetically significant JAB couplings differ by 25% (−10.2 vs −7.3 cm–1). This difference can be ascribed to three main contributions: (i) the central pyrazine ring shearing-like distortion, (ii) the effect of the orientation of the perchlorate counterions, and (iii) a hitherto unrecognized skeleton-counterion cooperation arising from different hydrogen bonding contributions in the two most significant JAB couplings. The impact of the orientation of the perchlorate counterions is disclosed by comparison to JAB studies using structurally similar ligands but with different electronegativity (namely, BF4–, BCl4–, and BBr4–). Pyrazine ligands and perchlorate counterions prove to be noninnocent.American Chemical Society2013info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/208012Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/https://doi.org/10.1021/ic400712sInorganic Chemistry, 2013, vol. 52, num.22, p. 12923-12932https://doi.org/https://doi.org/10.1021/ic400712s(c) American Chemical Society, 2013info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/2080122026-05-27T06:46:51Z
dc.title.none.fl_str_mv Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>
title Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>
spellingShingle Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>
Vela Llausí, Sergi
Propietats magnètiques
Lligands
Magnetisme
Magnetic properties
Ligands
Magnetism
title_short Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>
title_full Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>
title_fullStr Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>
title_full_unstemmed Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>
title_sort Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>
dc.creator.none.fl_str_mv Vela Llausí, Sergi
Jornet Somoza, Joaquim
Turnbull, Mark M.
Feyerherm, Ralf
Novoa Vide, Juan J.
Deumal i Solé, Mercè
author Vela Llausí, Sergi
author_facet Vela Llausí, Sergi
Jornet Somoza, Joaquim
Turnbull, Mark M.
Feyerherm, Ralf
Novoa Vide, Juan J.
Deumal i Solé, Mercè
author_role author
author2 Jornet Somoza, Joaquim
Turnbull, Mark M.
Feyerherm, Ralf
Novoa Vide, Juan J.
Deumal i Solé, Mercè
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Propietats magnètiques
Lligands
Magnetisme
Magnetic properties
Ligands
Magnetism
topic Propietats magnètiques
Lligands
Magnetisme
Magnetic properties
Ligands
Magnetism
description A complete first-principles bottom-up computational study of the magnetic properties of [Cu(pz)2](ClO4)2 is presented. A remarkable agreement is observed in the whole range of temperatures between simulated and experimental magnetic susceptibility data. Interestingly, the simulated heat capacity values show an anomaly close to the Néel temperature of 4.21 K associated with a transition from a two-dimensional (2D) antiferromagnet to a three-dimensional (3D) ordered state. The antiferromagnetic behavior of [Cu(pz)2](ClO4)2 is due to a 2D magnetic topology owing to two antiferromagnetic JAB interactions through pyrazine ligands. Although presenting a very similar molecular arrangement, the numerical values of the two magnetically significant JAB couplings differ by 25% (−10.2 vs −7.3 cm–1). This difference can be ascribed to three main contributions: (i) the central pyrazine ring shearing-like distortion, (ii) the effect of the orientation of the perchlorate counterions, and (iii) a hitherto unrecognized skeleton-counterion cooperation arising from different hydrogen bonding contributions in the two most significant JAB couplings. The impact of the orientation of the perchlorate counterions is disclosed by comparison to JAB studies using structurally similar ligands but with different electronegativity (namely, BF4–, BCl4–, and BBr4–). Pyrazine ligands and perchlorate counterions prove to be noninnocent.
publishDate 2013
dc.date.none.fl_str_mv 2013
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/208012
url https://hdl.handle.net/2445/208012
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/https://doi.org/10.1021/ic400712s
Inorganic Chemistry, 2013, vol. 52, num.22, p. 12923-12932
https://doi.org/https://doi.org/10.1021/ic400712s
dc.rights.none.fl_str_mv (c) American Chemical Society, 2013
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society, 2013
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 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 Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,301603

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