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Spin Crossover Behavior in a Series of Iron(III) Alkoxide Complexes

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Spin Crossover Behavior in a Series of Iron(III) Alkoxide Complexes

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dc.contributor.author Ortega Villar, Norma es_ES
dc.contributor.author Yesareth Guerrero-Estrada, Areli es_ES
dc.contributor.author Pineiro-Lopez, Lucia es_ES
dc.contributor.author Muñoz Roca, María del Carmen es_ES
dc.contributor.author Flores Alamo, Marcos es_ES
dc.contributor.author Moreno Esparza, Rafael es_ES
dc.contributor.author Real, Jose A. es_ES
dc.contributor.author Ugalde Saldivar, Victor M. es_ES
dc.date.accessioned 2016-09-30T07:57:11Z
dc.date.issued 2015-04
dc.identifier.issn 0020-1669
dc.identifier.uri http://hdl.handle.net/10251/70731
dc.description "This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/ic503081x es_ES
dc.description.abstract The synthesis, crystal structures, magnetic behavior, and electron paramagnetic resonance studies of five new FeIII spin crossover (SCO) complexes are reported. The [FeIIIN5O] coordination core is constituted of the pentadentate ligand bztpen (N5) and a series of alkoxide anions (ethoxide, propoxide, n-butoxide, isobutoxide, and ethylene glycoxide). The methoxide derivative previously reported by us is also reinvestigated. The six complexes crystallize in the orthorhombic Pbca space group and show similar molecular structures and crystal packing. The coordination octahedron is strongly distorted in both the high- and low-temperature structures. The structural changes upon spin conversion are consistent with those previously observed for [FeIIIN4O2] SCO complexes of the Schiff base type, except for the Fe−O(alkoxide) bond distance, which shortens significantly in the highspin state. Application of the Slichter−Drickamer thermodynamic model to the experimental SCO curves afforded reasonably good simulations with typical enthalpy and entropy variations ranging in the intervals ΔH = 6−13 kJ mol−1 and ΔS = 40−50 J mol−1 K−1 , respectively. The estimated values of the cooperativity parameter Γ, found in the interval 0−2.2 kJ mol−1 , were consistent with the nature of the SCO. Electron paramagnetic resonance spectroscopy confirmed the transformation between the high-spin and low-spin states, characterized by signals at g ≈ 4.47 and 2.10, respectively. Electrochemical analysis demonstrated the instability of the Fe(II) alkoxide derivatives in solution. es_ES
dc.description.sponsorship This work was supported by the Spanish Ministerio de Economia y Competitividad (MINECO) and FEDER funds (CTQ2013-46275-P) and Generalitat Valenciana (PROME-TEO/2012/049). L.P.-L. thanks the Generalitat Valenciana and Universitat de Valencia for a predoctoral fellowship. en_EN
dc.language Inglés es_ES
dc.publisher American Chemical Society es_ES
dc.relation Spanish Ministerio de Economia y Competitividad (MINECO) es_ES
dc.relation FEDER funds CTQ2013-46275-P es_ES
dc.relation Generalitat Valenciana PROME-TEO/2012/049 es_ES
dc.relation Generalitat Valenciana es_ES
dc.relation Universitat de Valencia es_ES
dc.relation.ispartof Inorganic Chemistry es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject SOLID-STATE es_ES
dc.subject MAGNETIC-SUSCEPTIBILITY es_ES
dc.subject PHASE-TRANSITIONS es_ES
dc.subject FERRIC COMPLEXES es_ES
dc.subject LIGAND; SYSTEM es_ES
dc.subject IRON es_ES
dc.subject MOSSBAUER es_ES
dc.subject SOLVATE es_ES
dc.subject FE(3-OET-SALAPA)2>(CLO4).S es_ES
dc.subject.classification FISICA APLICADA es_ES
dc.title Spin Crossover Behavior in a Series of Iron(III) Alkoxide Complexes es_ES
dc.type Artículo es_ES
dc.embargo.lift 10000-01-01
dc.embargo.terms forever es_ES
dc.identifier.doi 10.1021/ic503081x
dc.rights.accessRights Cerrado es_ES
dc.contributor.affiliation Universitat Politècnica de València. Departamento de Física Aplicada - Departament de Física Aplicada es_ES
dc.description.bibliographicCitation Ortega Villar, N.; Yesareth Guerrero-Estrada, A.; Pineiro-Lopez, L.; Muñoz Roca, MDC.; Flores Alamo, M.; Moreno Esparza, R.; Real, JA.... (2015). Spin Crossover Behavior in a Series of Iron(III) Alkoxide Complexes. Inorganic Chemistry. 54(7):3413-3421. doi:10.1021/ic503081x es_ES
dc.description.accrualMethod Senia es_ES
dc.relation.publisherversion http://pubs.acs.org/doi/abs/10.1021/ic503081x es_ES
dc.description.upvformatpinicio 3413 es_ES
dc.description.upvformatpfin 3421 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 54 es_ES
dc.description.issue 7 es_ES
dc.relation.senia 293080 es_ES
dc.identifier.eissn 1520-510X


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