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Homoleptic Iron(II) Complexes with the Ionogenic Ligand 6,6-Bis(1H-tetrazol-5-yl)-2,2'-bipyridine: Spin Crossover Behavior in a Singular 2D Spin Crossover Coordination Polymer

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Homoleptic Iron(II) Complexes with the Ionogenic Ligand 6,6-Bis(1H-tetrazol-5-yl)-2,2'-bipyridine: Spin Crossover Behavior in a Singular 2D Spin Crossover Coordination Polymer

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dc.contributor.author Seredyuk, Maksym es_ES
dc.contributor.author Piñeiro López, Lucia es_ES
dc.contributor.author Muñoz Roca, María del Carmen es_ES
dc.contributor.author Martínez Casado, Francisco J. es_ES
dc.contributor.author Molnár, Gábor es_ES
dc.contributor.author Rodriguez Velamazan, José Alberto es_ES
dc.contributor.author Bousseksou, Azzedine es_ES
dc.contributor.author Real, José Antonio es_ES
dc.date.accessioned 2016-09-30T08:19:37Z
dc.date.issued 2015-08
dc.identifier.issn 0020-1669
dc.identifier.uri http://hdl.handle.net/10251/70757
dc.description "This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Cemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b01001 es_ES
dc.description.abstract Deprotonation of the ionogenic tetradentate ligand 6,6'-bis(1H-tetrazol-5-yl)-2,2'-bipyridine [H(2)bipy(ttr)(2)] in the presence of Fe-II in solution has afforded an anionic mononuclear complex and a neutral two-dimensional coordination polymer formulated as, respectively, NEt3H{Fe[bipy(ttr)(2)][Hbipy(ttr)(2)]}center dot 3MeOH (1) and {Fe[bipy(ttr)(2)]}(n) (2). The anions [Hbipy(ttr)(2)](-) and [bipy(ttr)(2)](2-) embrace the Fe-II centers defining discrete molecular units 1 with the FeII ion lying in a distorted bisdisphenoid dodecahedron, a rare example of octacoordination in the coordination environment of this cation. The magnetic behavior of 1 shows that the FeII is high-spin, and its Mossbauer spectrum is characterized by a relatively large average quadrupole splitting, Delta E-Q = 3.42 mm s(-1). Compound 2 defines a strongly distorted octahedral environment for FeII in which one [bipy(ttr)(2)](-) anion coordinates the equatorial positions of the Fe-II center, while the axial positions are occupied by peripheral N-tetrazole atoms of two adjacent {Fe[bipy(ttr)(2)]}(0) moieties thereby generating an infinite double-layer sheet. Compound 2 undergoes an almost complete spin crossover transition between the high-spin and low-spin states centered at about 221 K characterized by an average variation of enthalpy and entropy Delta H-av = 8.27 kJ mol(-1), Delta S-av = 37.5 J K-1 mol(-1), obtained from calorimetric DSC measurements. Photomagnetic measurements of 2 at 10 K show an almost complete light-induced spin state trapping (LIESST) effect which denotes occurrence of antiferromagnetic coupling between the excited high-spin species and T-LIESST = 52 K. The crystal structure of 2 has been investigated in detail at various temperatures and discussed. es_ES
dc.description.sponsorship The research reported here was supported by the Spanish Ministerio de Economia y Competitividad (MINECO) and FEDER funds (CTQ2013-46275-P) and Generalitat Valenciana (PROMETEO/2012/049). L.P.-L. thanks the Generalitat Valenciana and the Universidad de Valencia for a predoctoral fellowship. M.S. thanks the EU for a Marie Curie fellowship (IIF-253254). 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 PROMETEO/2012/049 es_ES
dc.relation Generalitat Valenciana es_ES
dc.relation Universidad de Valencia es_ES
dc.relation EU IIF-253254 es_ES
dc.relation.ispartof Inorganic Chemistry es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject PHASE-TRANSITIONS es_ES
dc.subject SINGLE MOLECULES es_ES
dc.subject STATE es_ES
dc.subject COMPOUND es_ES
dc.subject MOSSBAUER es_ES
dc.subject PRESSURE es_ES
dc.subject CRYSTAL es_ES
dc.subject DEVICES es_ES
dc.subject SYSTEMS es_ES
dc.subject SYNERGY es_ES
dc.subject.classification FISICA APLICADA es_ES
dc.title Homoleptic Iron(II) Complexes with the Ionogenic Ligand 6,6-Bis(1H-tetrazol-5-yl)-2,2'-bipyridine: Spin Crossover Behavior in a Singular 2D Spin Crossover Coordination Polymer es_ES
dc.type Artículo es_ES
dc.embargo.lift 10000-01-01
dc.embargo.terms forever es_ES
dc.identifier.doi 10.1021/acs.inorgchem.5b01001
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 Seredyuk, M.; Piñeiro López, L.; Muñoz Roca, MDC.; Martínez Casado, FJ.; Molnár, G.; Rodriguez Velamazan, JA.; Bousseksou, A.... (2015). Homoleptic Iron(II) Complexes with the Ionogenic Ligand 6,6-Bis(1H-tetrazol-5-yl)-2,2'-bipyridine: Spin Crossover Behavior in a Singular 2D Spin Crossover Coordination Polymer. Inorganic Chemistry. 54(15):7424-7432. doi:10.1021/acs.inorgchem.5b01001 es_ES
dc.description.accrualMethod Senia es_ES
dc.relation.publisherversion http://dx.doi.org/10.1021/acs.inorgchem.5b01001 es_ES
dc.description.upvformatpinicio 7424 es_ES
dc.description.upvformatpfin 7432 es_ES
dc.type.version info:eu repo/semantics/publishedVersion es_ES
dc.description.volume 54 es_ES
dc.description.issue 15 es_ES
dc.relation.senia 293088 es_ES
dc.identifier.eissn 1520-510X


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