Afficher la notice abrégée

Series of M<sup>I</sup>[Co(bpy)<sub>3</sub>][Mo(CN)<sub>8</sub>]·<i>n</i>H<sub>2</sub>O (M<sup>I</sup> = Li (1), K (2), Rb (3), Cs (4); <i>n</i> = 7−8) exhibiting reversible diamagnetic to paramagnetic transition coupled with dehydration−rehydration process

hal.structure.identifierFaculty of Chemistry
dc.contributor.authorKOZIEL, Marcin
hal.structure.identifierFaculty of Chemistry
dc.contributor.authorPODGAJNY, Robert
hal.structure.identifierDepartment of Physics [SUPA]
dc.contributor.authorKANIA, Rafal
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorLE BRIS, Rémy
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMATHONIÈRE, Corine
hal.structure.identifierFaculty of Chemistry
dc.contributor.authorLEWINSKI, Krzysztof
hal.structure.identifierM. Smoluchowski Institute of Physics
dc.contributor.authorRAMS, Michal
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorLABRUGÈRE, Christine
hal.structure.identifierLaboratoire de chimie de coordination [LCC]
dc.contributor.authorBOUSSEKSOU, Azzedine
hal.structure.identifierFaculty of Chemistry
dc.contributor.authorSIEKLUCKA, Barbara
dc.date.issued2010
dc.identifier.issn0020-1669
dc.description.abstractEnIn this paper we report the synthesis and the structural and magnetic properties of the series of ionic compounds with general formula: M<sup>I</sup>[Co(bpy)<sub>3</sub>][Mo(CN)<sub>8</sub>]·<i>n</i>H<sub>2</sub>O (M<sup>I</sup> = Li, <i>n</i> = 8 (<b>1</b>), M<sup>I</sup> = K, <i>n</i> = 8 (<b>2</b>), M<sup>I</sup> = Rb, <i>n</i> = 8 (<b>3</b>), M<sup>I</sup> = Cs, <i>n</i> = 7.5 (<b>4</b>)). Solids <b>1</b>−<b>4</b> are characterized by the optical outer-sphere metal-to-metal charge transfer (MMCT) transition from Mo(IV) center to Co(III) center in the visible region and the Co<sup>III</sup>Mo<sup>IV</sup> Co<sup>II</sup>Mo<sup>V</sup> spin equilibrium strongly dominated by the Co<sup>III</sup>Mo<sup>IV</sup> form. We show a gentle thermal treatment of diamagnetic compounds <b>1</b>−<b>4</b> leading to the dehydrated forms <b>1a</b>−<b>4a</b>, which reveal a significant increase of paramagnetic contribution (from 0.5 to 2% to 30−40%). The rehydration allows to recover the diamagnetic phases <b>1b</b>−<b>4b</b> of compositions and properties similar to those of <b>1</b>−<b>4</b>. The irradiation of the dehydrated form <b>2a</b> within the MMCT band in the Superconducting Quantum Interference Device (SQUID) cavity at <i>T</i> = 10 K causes further increase of the Co<sup>II</sup>Mo<sup>V</sup> contribution giving the metastable phase annealed back to the <b>2a</b> phase after heating above <i>T</i> = 290 K. The IR, electron paramagnetic resonance (EPR), and X-ray photoelectron spectroscopy (XPS) spectroscopic data along with the magnetic data are interpreted in terms of strong modification of the Co<sup>III</sup>Mo<sup>IV</sup> Co<sup>II</sup>Mo<sup>V</sup> equilibrium occurring in these systems.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enSeries of M<sup>I</sup>[Co(bpy)<sub>3</sub>][Mo(CN)<sub>8</sub>]·<i>n</i>H<sub>2</sub>O (M<sup>I</sup> = Li (1), K (2), Rb (3), Cs (4); <i>n</i> = 7−8) exhibiting reversible diamagnetic to paramagnetic transition coupled with dehydration−rehydration process
dc.typeArticle de revue
dc.identifier.doi10.1021/ic901985z
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page2765-2772
bordeaux.volume49
bordeaux.issue6
bordeaux.peerReviewedoui
hal.identifierhal-00466927
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00466927v1
bordeaux.COinSctx_ver=Z39.88-2004&amp;rft_val_fmt=info:ofi/fmt:kev:mtx:journal&amp;rft.jtitle=Inorganic%20Chemistry&amp;rft.date=2010&amp;rft.volume=49&amp;rft.issue=6&amp;rft.spage=2765-2772&amp;rft.epage=2765-2772&amp;rft.eissn=0020-1669&amp;rft.issn=0020-1669&amp;rft.au=KOZIEL,%20Marcin&amp;PODGAJNY,%20Robert&amp;KANIA,%20Rafal&amp;LE%20BRIS,%20R%C3%A9my&amp;MATHONI%C3%88RE,%20Corine&amp;rft.genre=article


Fichier(s) constituant ce document

FichiersTailleFormatVue

Il n'y a pas de fichiers associés à ce document.

Ce document figure dans la(les) collection(s) suivante(s)

Afficher la notice abrégée