Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex

Reaction of a rigid tridentate ligand o-[(1H-imidazol-2-yl)methylideneamino]phenol (2-H(2)imap) with Co(ClO4) in the presence of NaN3, or Co(NO3)(2) without a base yields [Co-II(2-Himap)(2)] 1 and [Co-III(2-Himap) (2)]NO3 center dot MeOH2, respectively. Both complexes exhibit a mer-octahedral geomet...

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Autores: Sertphon, Darunee, Murray, Keith S., Phonsri, Wasinee, Jover Modrego, Jesús, Ruiz Sabín, Eliseo, Telfer, Shane G., Alkas, Adil, Harding, Phimphaka, Harding, David J.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/142923
Acceso en línea:https://hdl.handle.net/2445/142923
Access Level:acceso abierto
Palabra clave:Propietats magnètiques
Lligands (Bioquímica)
Magnetic properties
Ligands (Biochemistry)
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spelling Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complexSertphon, DaruneeMurray, Keith S.Phonsri, WasineeJover Modrego, JesúsRuiz Sabín, EliseoTelfer, Shane G.Alkas, AdilHarding, PhimphakaHarding, David J.Propietats magnètiquesLligands (Bioquímica)Magnetic propertiesLigands (Biochemistry)Reaction of a rigid tridentate ligand o-[(1H-imidazol-2-yl)methylideneamino]phenol (2-H(2)imap) with Co(ClO4) in the presence of NaN3, or Co(NO3)(2) without a base yields [Co-II(2-Himap)(2)] 1 and [Co-III(2-Himap) (2)]NO3 center dot MeOH2, respectively. Both complexes exhibit a mer-octahedral geometry with the cobalt centre being distorted along an octahedral-trigonal prismatic pathway. The packing in 1 and 2 is dominated by H-bonding forming 2D sheets and 1D chains, respectively. Detailed dc and ac magnetic studies indicate that 1 is a field-induced single-ion magnet (SIM) with D = 36.7 cm(-1) and E = 2.0 cm(-1). Extensive ab initio calculations support these conclusions and suggest that relaxation of the magnetization occurs principally through direct quantum tunnelling in the ground state, with the Raman process dominant in an applied field. This contrasts with the recently reported series of mer-[Co(L)(2)] (L = monoanionic NNO donor ligand; Inorg. Chem., 2017, 56, 6056-6066) complexes where D is negative, as these compounds have a more ambiguous geometry, and highlights the importance of supramolecular interactions in subtly altering the coordination sphere thereby impacting the magnetic behaviour.Royal Society of Chemistry2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/142923Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1039/c7dt04335jDalton Transactions, 2018, vol. 47, num. 3, p. 859-867https://doi.org/10.1039/c7dt04335j(c) Sertphon, Darunee et al., 2018info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1429232026-05-27T06:46:51Z
dc.title.none.fl_str_mv Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
title Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
spellingShingle Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
Sertphon, Darunee
Propietats magnètiques
Lligands (Bioquímica)
Magnetic properties
Ligands (Biochemistry)
title_short Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
title_full Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
title_fullStr Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
title_full_unstemmed Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
title_sort Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
dc.creator.none.fl_str_mv Sertphon, Darunee
Murray, Keith S.
Phonsri, Wasinee
Jover Modrego, Jesús
Ruiz Sabín, Eliseo
Telfer, Shane G.
Alkas, Adil
Harding, Phimphaka
Harding, David J.
author Sertphon, Darunee
author_facet Sertphon, Darunee
Murray, Keith S.
Phonsri, Wasinee
Jover Modrego, Jesús
Ruiz Sabín, Eliseo
Telfer, Shane G.
Alkas, Adil
Harding, Phimphaka
Harding, David J.
author_role author
author2 Murray, Keith S.
Phonsri, Wasinee
Jover Modrego, Jesús
Ruiz Sabín, Eliseo
Telfer, Shane G.
Alkas, Adil
Harding, Phimphaka
Harding, David J.
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Propietats magnètiques
Lligands (Bioquímica)
Magnetic properties
Ligands (Biochemistry)
topic Propietats magnètiques
Lligands (Bioquímica)
Magnetic properties
Ligands (Biochemistry)
description Reaction of a rigid tridentate ligand o-[(1H-imidazol-2-yl)methylideneamino]phenol (2-H(2)imap) with Co(ClO4) in the presence of NaN3, or Co(NO3)(2) without a base yields [Co-II(2-Himap)(2)] 1 and [Co-III(2-Himap) (2)]NO3 center dot MeOH2, respectively. Both complexes exhibit a mer-octahedral geometry with the cobalt centre being distorted along an octahedral-trigonal prismatic pathway. The packing in 1 and 2 is dominated by H-bonding forming 2D sheets and 1D chains, respectively. Detailed dc and ac magnetic studies indicate that 1 is a field-induced single-ion magnet (SIM) with D = 36.7 cm(-1) and E = 2.0 cm(-1). Extensive ab initio calculations support these conclusions and suggest that relaxation of the magnetization occurs principally through direct quantum tunnelling in the ground state, with the Raman process dominant in an applied field. This contrasts with the recently reported series of mer-[Co(L)(2)] (L = monoanionic NNO donor ligand; Inorg. Chem., 2017, 56, 6056-6066) complexes where D is negative, as these compounds have a more ambiguous geometry, and highlights the importance of supramolecular interactions in subtly altering the coordination sphere thereby impacting the magnetic behaviour.
publishDate 2018
dc.date.none.fl_str_mv 2018
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/2445/142923
url https://hdl.handle.net/2445/142923
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/10.1039/c7dt04335j
Dalton Transactions, 2018, vol. 47, num. 3, p. 859-867
https://doi.org/10.1039/c7dt04335j
dc.rights.none.fl_str_mv (c) Sertphon, Darunee et al., 2018
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Sertphon, Darunee et al., 2018
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 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 (Química Inorgànica i Orgànica)
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 15.300719

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