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hal.structure.identifierFaculty of Chemistry
dc.contributor.authorKOZNEKIAK, Tomasz
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDESPLANCHES, Cédric
hal.structure.identifierFaculty of Chemistry
dc.contributor.authorPODGAJNY, Robert
hal.structure.identifierInstitute for Material Science
dc.contributor.authorGIMÉNEZ-SAIZ, Carlos
hal.structure.identifierM. Smoluchowski Institute of Physics
dc.contributor.authorRAMS, Michal
hal.structure.identifierFaculty of Chemistry
dc.contributor.authorSIEKLUCKA, Barbara
dc.date.issued2009
dc.identifier.issn0020-1669
dc.description.abstractEnWe report on the syntheses, crystal structures, and magnetic properties of two cyano-bridged molecular assemblies: [Cu<sup>II</sup>(phen)<sub>3</sub>]<sub>2</sub>{[Cu<sup>II</sup>(phen)<sub>2</sub>]<sub>2</sub>[W<sup>V</sup>(CN)<sub>8</sub>]<sub>2</sub>}(ClO<sub>4</sub>)<sub>2</sub>·10H<sub>2</sub>O (phen = 1,10-phenanthroline) (<b>1</b>) and {[Cu<sup>II</sup>(bpy)<sub>2</sub>]<sub>2</sub>[W<sup>V</sup>(CN)<sub>8</sub>]} {[Cu<sup>II</sup>(bpy)<sub>2</sub>][W<sup>V</sup>(CN)<sub>8</sub>]}·4H<sub>2</sub>O (bpy = 2,2′-bipyridyl) (<b>2</b>). Compound <b>1</b> consists of cyano-bridged [Cu<sup>II</sup><sub>2</sub>W<sup>V</sup><sub>2</sub>]<sup>2−</sup> molecular rectangles and isolated [Cu<sup>II</sup>(phen)<sub>3</sub>]<sup>2+</sup> complexes. The molecular structure of <b>2</b> reveals cyano-bridged trinuclear [Cu<sup>II</sup><sub>2</sub>W<sup>V</sup>]<sup>+</sup> and dinuclear [Cu<sup>II</sup>W<sup>V</sup>]<sup>−</sup> ions. Magnetic interactions in <b>1</b> are interpreted in terms of the model of a tetranuclear moiety consisting of two ferromagnetic Cu<sup>II</sup>−NC−W<sup>V</sup> units (<i>J</i><sub>1</sub> = +39(4) cm<sup>−1</sup>) interacting antiferromagnetically (<i>J</i><sub>2</sub> = −1.6(4) cm<sup>−1</sup>). The analysis of the magnetic response of <b>2</b> reveals ferromagnetic interaction within the [Cu<sup>II</sup>−NC−W<sup>V</sup>−CN−Cu<sup>II</sup>]<sup>+</sup> and [Cu<sup>II</sup>−NC−W<sup>V</sup>]<sup>−</sup> isolated units, characterized by <i>J</i> = +35(7) cm<sup>−1</sup> and antiferromagnetic coupling between them (4<i>J</i>′ = −0.30(8) cm<sup>−1</sup>). The discussion of the magnetic behavior and the correlation of the <i>J</i><sub>CuW</sub> parameters with the geometry of cyano bridges at copper(II) centers of <b>1</b> and <b>2</b> is based on the DFT calculations, which yield <i>J</i><sub>av</sub> = +13.2 cm<sup>−1</sup> for <b>1</b> and <i>J</i> = +31 cm<sup>−1</sup> for <b>2</b>. The domination of the ferromagnetic Cu<sup>II</sup>−NC−W<sup>V</sup> interaction in <b>1</b> and <b>2</b> originates from the mutual orthogonality of natural magnetic orbitals in the case of coordination of cyano bridges at the equatorial sites of Cu(II) moieties.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subject.enChemical synthesis
dc.subject.enCrystal structure
dc.subject.enMagnetic properties
dc.subject.enCyano bridged molecular assemblies
dc.typeArticle de revue
dc.identifier.doi10.1021/ic801989b
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page2865-2872
bordeaux.volume48
bordeaux.issue7
bordeaux.peerReviewedoui
hal.identifierhal-00374044
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00374044v1
bordeaux.COinSctx_ver=Z39.88-2004&amp;rft_val_fmt=info:ofi/fmt:kev:mtx:journal&amp;rft.jtitle=Inorganic%20Chemistry&amp;rft.date=2009&amp;rft.volume=48&amp;rft.issue=7&amp;rft.spage=2865-2872&amp;rft.epage=2865-2872&amp;rft.eissn=0020-1669&amp;rft.issn=0020-1669&amp;rft.au=KOZNEKIAK,%20Tomasz&amp;DESPLANCHES,%20C%C3%A9dric&amp;PODGAJNY,%20Robert&amp;GIM%C3%89NEZ-SAIZ,%20Carlos&amp;RAMS,%20Michal&amp;rft.genre=article


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