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. https://doi.org/10.1021/acs.inorgchem.5b01001
Por favor, use este identificador para citar o enlazar este ítem: http://hdl.handle.net/10251/70757
Título:
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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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Autor:
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Seredyuk, Maksym
Piñeiro López, Lucia
Muñoz Roca, María del Carmen
Martínez Casado, Francisco J.
Molnár, Gábor
Rodriguez Velamazan, José Alberto
Bousseksou, Azzedine
Real, José Antonio
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Entidad UPV:
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Universitat Politècnica de València. Departamento de Física Aplicada - Departament de Física Aplicada
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Fecha difusión:
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Resumen:
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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 ...[+]
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.
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Palabras clave:
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PHASE-TRANSITIONS
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SINGLE MOLECULES
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STATE
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COMPOUND
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MOSSBAUER
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PRESSURE
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CRYSTAL
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DEVICES
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SYSTEMS
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SYNERGY
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Derechos de uso:
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Cerrado |
Fuente:
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Inorganic Chemistry. (issn:
0020-1669
) (eissn:
1520-510X
)
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DOI:
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10.1021/acs.inorgchem.5b01001
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Editorial:
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American Chemical Society
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Versión del editor:
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http://dx.doi.org/10.1021/acs.inorgchem.5b01001
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Código del Proyecto:
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info:eu-repo/grantAgreement/MINECO//CTQ2013-46275-P/ES/SENSORES Y MEMORIAS BASADOS EN MATERIALES BIESTABLES CON TRANSICION DE ESPIN/
info:eu-repo/grantAgreement/EC/FP7/253254/EU/Tailoring crossover properties by electric field in nano-structural and liquid crystalline molecular based magnetic materials/ELECTROSCO/
info:eu-repo/grantAgreement/GVA//PROMETEO%2F2012%2F049/
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Descripción:
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"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
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Agradecimientos:
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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 ...[+]
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).
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Tipo:
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Artículo
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