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Supramolecular iron metallocubanes exhibiting site-selective thermal and light-induced spin-crossover

hal.structure.identifierSchool of Chemistry [Leeds]
dc.contributor.authorBERDIELL, Izar Capel
hal.structure.identifierDepartment of Physics
dc.contributor.authorHOCHDÖRFFER, Tim
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDESPLANCHES, Cédric
hal.structure.identifierSchool of Chemistry [Leeds]
dc.contributor.authorKULMACZEWSKI, Rafal
hal.structure.identifierSchool of Chemistry [Leeds]
dc.contributor.authorSHAHID, Namrah
hal.structure.identifierDepartment of Physics
dc.contributor.authorWOLNY, Juliusz
hal.structure.identifierSchool of Chemistry [Leeds]
dc.contributor.authorWARRINER, Stuart
hal.structure.identifierSchool of Physics and Astronomy [Leeds]
dc.contributor.authorCESPEDES, Oscar
hal.structure.identifierDepartment of Physics
dc.contributor.authorSCHÜNEMANN, Volker
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorCHASTANET, Guillaume
hal.structure.identifierSchool of Chemistry [Leeds]
dc.contributor.authorHALCROW, Malcolm
dc.date.issued2019-11-08
dc.identifier.issn0002-7863
dc.description.abstractEnTreatment of Fe[BF4]2·6H2O with 4,6-di(pyrazol-1-yl)-1H-pyrimid-2-one (HL1) or 4,6-di(4-methylpyrazol-1-yl)-1H-pyrimid-2-one (HL2) affords solvated crystals of [{FeIII(OH2)6}⊂FeII8(μ-L)12][BF4]7 (1, HL = HL1; 2, HL = HL2). The centrosymmetric complexes contain a cubic arrangement of iron(II) centers, with bis-bidentate [L]− ligands bridging the edges of the cube. The encapsulated [Fe(OH2)6]3+ moiety templates the assembly through 12 O–H···O hydrogen bonds to the [L]− hydroxylate groups. All four unique iron(II) ions in the cages are crystallographically high-spin at 250 K, but they undergo a gradual high → low spin-crossover on cooling, which is predominantly centered on one iron(II) site and its symmetry-related congener. This was confirmed by magnetic susceptibility data, light-induced excited spin state trapping (LIESST) effect measurements, and, for 1, Mössbauer spectroscopy and diffuse reflectance data. The clusters are stable in MeCN solution, and 1 remains high-spin above 240 K in that solvent. The cubane assembly was not obtained from reactions using other iron(II) salts or 4,6-di(pyrazol-1-yl)pyrimidine ligands, highlighting the importance of hydrogen bonding in templating the cubane assembly.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enSupramolecular iron metallocubanes exhibiting site-selective thermal and light-induced spin-crossover
dc.typeArticle de revue
dc.identifier.doi10.1021/jacs.9b08862
dc.subject.halChimie/Matériaux
bordeaux.journalJournal of the American Chemical Society
bordeaux.page18759-18770
bordeaux.volume141
bordeaux.issue47
bordeaux.peerReviewedoui
hal.identifierhal-02383213
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-02383213v1
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