Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study

Compounds [Co(L-N4R2)(dbdiox)](BPh4) (L-N4R2 = N,N′-di-alkyl-2,11-diaza[3.3]-(2,6)pyridinophane, R = iPr (1a), Et (2a); dbdiox = 3,5-di-tert-butyldioxolene) and [M(L-N4iPr2)(dbdiox)](BPh4) (M = Mn (3a), Fe (4a)) have been synthesized and investigated with a view to possible valence tautomeric (VT) o...

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Autores: Tezgerevska, Tina, Rousset, Elodie, Gable, Robert W., Jameson, Guy N. L., Sañudo Zotes, Eva Carolina, Starikova, Alyona A., Boskovic, Colette
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
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:2445/139428
Acesso em linha:https://hdl.handle.net/2445/139428
Access Level:acceso abierto
Palavra-chave:Complexos metàl·lics
Metal complexes
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spelling Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational studyTezgerevska, TinaRousset, ElodieGable, Robert W.Jameson, Guy N. L.Sañudo Zotes, Eva CarolinaStarikova, Alyona A.Boskovic, ColetteComplexos metàl·licsMetal complexesCompounds [Co(L-N4R2)(dbdiox)](BPh4) (L-N4R2 = N,N′-di-alkyl-2,11-diaza[3.3]-(2,6)pyridinophane, R = iPr (1a), Et (2a); dbdiox = 3,5-di-tert-butyldioxolene) and [M(L-N4iPr2)(dbdiox)](BPh4) (M = Mn (3a), Fe (4a)) have been synthesized and investigated with a view to possible valence tautomeric (VT) or spin crossover (SCO) interconversions. Single crystal X-ray diffraction data for all compounds at 100 or 130 K indicate trivalent metal cations and di-tert-butylcatecholate (dbcat2−) dioxolene ligands. Variable temperature magnetic susceptibility data for all species between 2 and 340 K are consistent with these redox states, with low spin configurations for the cobalt(III) ions and high spin for the manganese(III) and iron(III) ions. Above 340 K, compound 1a exhibits an increase in magnetic susceptibility, suggesting the onset of a VT interconversion from low spin Co(III)-dbcat to high spin Co(II)-dbsq (dbsq− = di-tert-butylsemiquinonate) that is incomplete up to 400 K. In solution, variable temperature electronic absorption spectra and Evans NMR method magnetic susceptibility data indicate reversible VT interconversions for 1a in several solvents, with the transition temperature varying with solvent. Variable temperature electronic absorption spectra are temperature-invariant for 3a and 4a, while spectra for 2a in 1,2-dichloroethane suggest the onset of a VT transition at the highest temperatures measured. Density functional theory calculations on all four compounds and literature analogues provide key insights into the relative energies of the different electromeric forms and the possibilities for VT versus SCO interconversions in this family of compounds.Royal Society of Chemistry2019202020192019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion16 p.application/pdfhttps://hdl.handle.net/2445/139428Articles publicats en revistes (Química Inorgànica i Orgànica)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/10.1039/C9DT02372KDalton Transactions, 2019, vol. 48, num. 31, p. 11674-11689https://doi.org/10.1039/C9DT02372K(c) Tezgerevska, Tina et al., 2019info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1394282026-05-29T05:05:01Z
dc.title.none.fl_str_mv Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
title Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
spellingShingle Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
Tezgerevska, Tina
Complexos metàl·lics
Metal complexes
title_short Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
title_full Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
title_fullStr Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
title_full_unstemmed Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
title_sort Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
dc.creator.none.fl_str_mv Tezgerevska, Tina
Rousset, Elodie
Gable, Robert W.
Jameson, Guy N. L.
Sañudo Zotes, Eva Carolina
Starikova, Alyona A.
Boskovic, Colette
author Tezgerevska, Tina
author_facet Tezgerevska, Tina
Rousset, Elodie
Gable, Robert W.
Jameson, Guy N. L.
Sañudo Zotes, Eva Carolina
Starikova, Alyona A.
Boskovic, Colette
author_role author
author2 Rousset, Elodie
Gable, Robert W.
Jameson, Guy N. L.
Sañudo Zotes, Eva Carolina
Starikova, Alyona A.
Boskovic, Colette
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Complexos metàl·lics
Metal complexes
topic Complexos metàl·lics
Metal complexes
description Compounds [Co(L-N4R2)(dbdiox)](BPh4) (L-N4R2 = N,N′-di-alkyl-2,11-diaza[3.3]-(2,6)pyridinophane, R = iPr (1a), Et (2a); dbdiox = 3,5-di-tert-butyldioxolene) and [M(L-N4iPr2)(dbdiox)](BPh4) (M = Mn (3a), Fe (4a)) have been synthesized and investigated with a view to possible valence tautomeric (VT) or spin crossover (SCO) interconversions. Single crystal X-ray diffraction data for all compounds at 100 or 130 K indicate trivalent metal cations and di-tert-butylcatecholate (dbcat2−) dioxolene ligands. Variable temperature magnetic susceptibility data for all species between 2 and 340 K are consistent with these redox states, with low spin configurations for the cobalt(III) ions and high spin for the manganese(III) and iron(III) ions. Above 340 K, compound 1a exhibits an increase in magnetic susceptibility, suggesting the onset of a VT interconversion from low spin Co(III)-dbcat to high spin Co(II)-dbsq (dbsq− = di-tert-butylsemiquinonate) that is incomplete up to 400 K. In solution, variable temperature electronic absorption spectra and Evans NMR method magnetic susceptibility data indicate reversible VT interconversions for 1a in several solvents, with the transition temperature varying with solvent. Variable temperature electronic absorption spectra are temperature-invariant for 3a and 4a, while spectra for 2a in 1,2-dichloroethane suggest the onset of a VT transition at the highest temperatures measured. Density functional theory calculations on all four compounds and literature analogues provide key insights into the relative energies of the different electromeric forms and the possibilities for VT versus SCO interconversions in this family of compounds.
publishDate 2019
dc.date.none.fl_str_mv 2019
2019
2019
2020
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/2445/139428
url https://hdl.handle.net/2445/139428
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/C9DT02372K
Dalton Transactions, 2019, vol. 48, num. 31, p. 11674-11689
https://doi.org/10.1039/C9DT02372K
dc.rights.none.fl_str_mv (c) Tezgerevska, Tina et al., 2019
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Tezgerevska, Tina et al., 2019
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 16 p.
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: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 15.811543

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