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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.identifier | Faculty of Chemistry | |
| dc.contributor.author | KOZIEL, Marcin | |
| hal.structure.identifier | Faculty of Chemistry | |
| dc.contributor.author | PODGAJNY, Robert | |
| hal.structure.identifier | Department of Physics [SUPA] | |
| dc.contributor.author | KANIA, Rafal | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | LE BRIS, Rémy | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | MATHONIÈRE, Corine | |
| hal.structure.identifier | Faculty of Chemistry | |
| dc.contributor.author | LEWINSKI, Krzysztof | |
| dc.contributor.author | RAMS, Michal | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | LABRUGÈRE, Christine | |
| hal.structure.identifier | Laboratoire de chimie de coordination [LCC] | |
| dc.contributor.author | BOUSSEKSOU, Azzedine | |
| hal.structure.identifier | Faculty of Chemistry | |
| dc.contributor.author | SIEKLUCKA, Barbara | |
| dc.date.issued | 2010 | |
| dc.identifier.issn | 0020-1669 | |
| dc.description.abstractEn | In 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.iso | en | |
| dc.publisher | American Chemical Society | |
| dc.title.en | 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 | |
| dc.type | Article de revue | |
| dc.identifier.doi | 10.1021/ic901985z | |
| dc.subject.hal | Chimie/Matériaux | |
| bordeaux.journal | Inorganic Chemistry | |
| bordeaux.page | 2765-2772 | |
| bordeaux.volume | 49 | |
| bordeaux.issue | 6 | |
| bordeaux.peerReviewed | oui | |
| hal.identifier | hal-00466927 | |
| hal.version | 1 | |
| hal.popular | non | |
| hal.audience | Internationale | |
| hal.origin.link | https://hal.archives-ouvertes.fr//hal-00466927v1 | |
| bordeaux.COinS | ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Inorganic%20Chemistry&rft.date=2010&rft.volume=49&rft.issue=6&rft.spage=2765-2772&rft.epage=2765-2772&rft.eissn=0020-1669&rft.issn=0020-1669&rft.au=KOZIEL,%20Marcin&PODGAJNY,%20Robert&KANIA,%20Rafal&LE%20BRIS,%20R%C3%A9my&MATHONI%C3%88RE,%20Corine&rft.genre=article |
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