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Radical−Radical Recognition: Switchable Magnetic Properties and Re-entrant Behavior

hal.structure.identifierDepartment of Chemistry, University of Guelph
dc.contributor.authorM. FATILA, Elisabeth
hal.structure.identifierDepartment of Chemistry, University of Guelph
dc.contributor.authorR., Alex Mayo
hal.structure.identifierCentre de recherches Paul Pascal [CRPP]
dc.contributor.authorROUZIÈRES, Mathieu
hal.structure.identifierFreeLance Crystallography
dc.contributor.authorC. JENNINGS, Michael
hal.structure.identifierCentre de recherches Paul Pascal [CRPP]
dc.contributor.authorDECHAMBENOIT, Pierre
hal.structure.identifierDepartment of Chemistry, University of Guelph
dc.contributor.authorSOLDATOV, Dmitry V.
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMATHONIÈRE, Corine
hal.structure.identifierCentre de recherches Paul Pascal [CRPP]
dc.contributor.authorCLÉRAC, Rodolphe
hal.structure.identifierCentre de recherches Paul Pascal [CRPP]
dc.contributor.authorCOULON, Claude
hal.structure.identifierDepartment of Chemistry, University of Guelph
dc.contributor.authorE. PREUSS, Kathryn
dc.date.issued2015-05-05
dc.identifier.issn0897-4756
dc.description.abstractEnπ−π radical interactions have exacting geometry requirements, significantly more stringent than those of a hydrogen bond or a van der Waals interaction. Here, supramolecular synthons based on such radical−radical recognition are employed to generate switchable structuraland magnetic properties. Interactions between neighboring paramagnetic ligands of the La(hfac)3(pyDTDA)2 coordination complex cause a rare re-entrant phase transition (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato-; pyDTDA = 4-(2′-pyridyl)- 1,2,3,5-dithiadiazolyl). Below 100 K, the complex is diamagnetic in the solid state, consistent with an f 0 lanthanum(III) ion and “pancake bonding” of the π-radical ligands. Upon heating, the supramolecular one-dimensional arrangement undergoes two sequential structural phase transitions, observed at ca. 160 and 310 K, successively involving the rupture of half and then the totality of the “pancake bonds” and generating stepwise increases in the paramagnetic susceptibility. We use the structural and magnetic data to develop a theoretical model that clearly predicts the unprecedented re-entrant behavior of this radical-La(III)-radical complex. Moreover, this microscopic free-energy model demonstrates that any system with essentially noninteracting “dimers” contains within itself the possibility of a distortion associated with re-entrant phase transitions if the lattice is “soft” enough (i.e., low rigidity).
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enRadical−Radical Recognition: Switchable Magnetic Properties and Re-entrant Behavior
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.chemmater.5b00967
dc.subject.halChimie/Matériaux
bordeaux.journalChemistry of Materials
bordeaux.pagepp. 4023-4032
bordeaux.volume27
bordeaux.issue11
bordeaux.peerReviewedoui
hal.identifierhal-01162012
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01162012v1
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