Dynamical effects on the magnetic properties of dithiazolyl bistable materials

The magnetic properties of molecule-based magnets are commonly rationalized by considering only a single nuclear configuration of the system under study (usually an X-ray crystal structure). Here, by means of a computational study, we compare the results obtained using such a static approach with th...

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Autores: Vela Llausí, Sergi, Deumal i Solé, Mercè, Shiga, Motoyuki, Novoa Vide, Juan J., Ribas Ariño, Jordi
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2015
País:España
Institución: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:2445/173005
Acceso en línea:https://hdl.handle.net/2445/173005
Access Level:acceso abierto
Palabra clave:Cristalls
Propietats magnètiques
Crystals
Magnetic properties
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spelling Dynamical effects on the magnetic properties of dithiazolyl bistable materialsVela Llausí, SergiDeumal i Solé, MercèShiga, MotoyukiNovoa Vide, Juan J.Ribas Ariño, JordiCristallsPropietats magnètiquesCrystalsMagnetic propertiesThe magnetic properties of molecule-based magnets are commonly rationalized by considering only a single nuclear configuration of the system under study (usually an X-ray crystal structure). Here, by means of a computational study, we compare the results obtained using such a static approach with those obtained by explicitly accounting for thermal fluctuations, and uncover the serious limitations of the static perspective when dealing with magnetic crystals whose radicals undergo wide-amplitude motions. As a proof of concept, these limitations are illustrated for the magnetically bistable 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) material. For its high-temperature phase at 300 K, we show that nuclear dynamics induce large fluctuations in the magnetic exchange interactions (JAB) between spins (up to 1000% of the average value). These deviations result in a ∼20% difference between the 300 K magnetic susceptibility computed by explicitly considering the nuclear dynamics and that computed using the X-ray structure, the former being in better agreement with the experimental data. The unveiled strong coupling between JAB interactions and intermolecular vibrations reveals that considering JAB as a constant value at a given temperature (as always done in molecular magnetism) leads to a flawed description of the magnetism of TTTA. Instead, the physically relevant concept in this case is the statistical distribution of JAB values. The discovery that a single X-ray structure is not adequate enough to interpret the magnetic properties of TTTA is also expected to be decisive in other organic magnets with dominant exchange interactions propagating through labile π-π networks.Royal Society of Chemistry2021202120152021info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersion11 p.application/pdfapplication/pdfhttps://hdl.handle.net/2445/173005Articles 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)InglésReproducció del document publicat a: https://doi.org/10.1039/c4sc03930kChemical Science, 2015, vol. 6, num. 4, p. 2371-2381https://doi.org/10.1039/c4sc03930kcc-by (c) Vela Llausí, Sergi et al., 2015http://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1730052026-05-29T05:05:01Z
dc.title.none.fl_str_mv Dynamical effects on the magnetic properties of dithiazolyl bistable materials
title Dynamical effects on the magnetic properties of dithiazolyl bistable materials
spellingShingle Dynamical effects on the magnetic properties of dithiazolyl bistable materials
Vela Llausí, Sergi
Cristalls
Propietats magnètiques
Crystals
Magnetic properties
title_short Dynamical effects on the magnetic properties of dithiazolyl bistable materials
title_full Dynamical effects on the magnetic properties of dithiazolyl bistable materials
title_fullStr Dynamical effects on the magnetic properties of dithiazolyl bistable materials
title_full_unstemmed Dynamical effects on the magnetic properties of dithiazolyl bistable materials
title_sort Dynamical effects on the magnetic properties of dithiazolyl bistable materials
dc.creator.none.fl_str_mv Vela Llausí, Sergi
Deumal i Solé, Mercè
Shiga, Motoyuki
Novoa Vide, Juan J.
Ribas Ariño, Jordi
author Vela Llausí, Sergi
author_facet Vela Llausí, Sergi
Deumal i Solé, Mercè
Shiga, Motoyuki
Novoa Vide, Juan J.
Ribas Ariño, Jordi
author_role author
author2 Deumal i Solé, Mercè
Shiga, Motoyuki
Novoa Vide, Juan J.
Ribas Ariño, Jordi
author2_role author
author
author
author
dc.subject.none.fl_str_mv Cristalls
Propietats magnètiques
Crystals
Magnetic properties
topic Cristalls
Propietats magnètiques
Crystals
Magnetic properties
description The magnetic properties of molecule-based magnets are commonly rationalized by considering only a single nuclear configuration of the system under study (usually an X-ray crystal structure). Here, by means of a computational study, we compare the results obtained using such a static approach with those obtained by explicitly accounting for thermal fluctuations, and uncover the serious limitations of the static perspective when dealing with magnetic crystals whose radicals undergo wide-amplitude motions. As a proof of concept, these limitations are illustrated for the magnetically bistable 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) material. For its high-temperature phase at 300 K, we show that nuclear dynamics induce large fluctuations in the magnetic exchange interactions (JAB) between spins (up to 1000% of the average value). These deviations result in a ∼20% difference between the 300 K magnetic susceptibility computed by explicitly considering the nuclear dynamics and that computed using the X-ray structure, the former being in better agreement with the experimental data. The unveiled strong coupling between JAB interactions and intermolecular vibrations reveals that considering JAB as a constant value at a given temperature (as always done in molecular magnetism) leads to a flawed description of the magnetism of TTTA. Instead, the physically relevant concept in this case is the statistical distribution of JAB values. The discovery that a single X-ray structure is not adequate enough to interpret the magnetic properties of TTTA is also expected to be decisive in other organic magnets with dominant exchange interactions propagating through labile π-π networks.
publishDate 2015
dc.date.none.fl_str_mv 2015
2021
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/173005
url https://hdl.handle.net/2445/173005
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.1039/c4sc03930k
Chemical Science, 2015, vol. 6, num. 4, p. 2371-2381
https://doi.org/10.1039/c4sc03930k
dc.rights.none.fl_str_mv cc-by (c) Vela Llausí, Sergi et al., 2015
http://creativecommons.org/licenses/by/3.0/es/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc-by (c) Vela Llausí, Sergi et al., 2015
http://creativecommons.org/licenses/by/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 11 p.
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 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

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