Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)2](ClO4)2

Vela Llausí, Sergi; Jornet Somoza, Joaquim; Turnbull, Mark M.; Feyerherm, Ralf; Novoa Vide, Juan J.; Deumal i Solé, Mercè

Dividing the Spoils: Role of Pyrazine Ligands and Perchlorate Counterions in the Magnetic Properties of Bis(pyrazine)diperchloratecopper(II), [Cu(pz)2](ClO4)2

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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Detalhes bibliográficos
Autores:	Vela Llausí, Sergi, Jornet Somoza, Joaquim, Turnbull, Mark M., Feyerherm, Ralf, Novoa Vide, Juan J., Deumal i Solé, Mercè
Formato:	artículo
Estado:	Versión aceptada para publicación
Fecha de publicación:	2013
País:	España
Recursos:	Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:	Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:	oai:recercat.cat:2445/208012
Acesso em linha:	https://hdl.handle.net/2445/208012
Access Level:	acceso abierto
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 Society2024202420132024info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion10 p.application/pdfapplication/pdfhttps://hdl.handle.net/2445/208012Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió 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:recercat.cat:2445/2080122026-05-29T05:05:01Z
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 2024 2024 2024
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	10 p. 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	Articles publicats en revistes (Ciència dels Materials i Química Física) reponame:Recercat. Dipósit de la Recerca de Catalunya instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str	Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str	Recercat. Dipósit de la Recerca de Catalunya
collection	Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score	15.812429

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>

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