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Decoupled spin crossover and structural phase transition in a molecular iron(II) complex

hal.structure.identifierSchool of Chemistry [Leeds]
dc.contributor.authorKERSHAW COOK, Laurence J.
hal.structure.identifierDepartment of Chemistry
dc.contributor.authorSHEPHERD, Helena
hal.structure.identifierInstitute for Materials Research
dc.contributor.authorCOMYN, Tim P.
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierSciences and Technology Department
dc.contributor.authorBALDÉ, Chérif
hal.structure.identifierSchool of Physics and Astronomy [Leeds]
dc.contributor.authorCESPEDES, Oscar
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 A
dc.date.issued2015
dc.identifier.issn0947-6539
dc.description.abstractEnCrystalline [Fe(bppSMe)2 ][BF4 ]2 (1; bppSMe=4-(methylsulfanyl)-2,6-di(pyrazol-1-yl)pyridine) undergoes an abrupt spin-crossover (SCO) event at 265±5 K. The crystals also undergo a separate phase transition near 205 K, involving a contraction of the unit-cell a axis to one-third of its original value (high-temperature phase 1; Pbcn, Z=12; low-temperature phase 2; Pbcn, Z=4). The SCO-active phase 1 contains two unique molecular environments, one of which appears to undergo SCO more gradually than the other. In contrast, powder samples of 1 retain phase 1 between 140-300 K, although their SCO behaviour is essentially identical to the single crystals. The compounds [Fe(bppBr)2 ][BF4 ]2 (2; bppBr=4-bromo-2,6-di(pyrazol-1-yl)pyridine) and [Fe(bppI)2 ][BF4 ]2 (3; bppI=4-iodo-2,6-di(pyrazol-1-yl)-pyridine) exhibit more gradual SCO near room temperature, and adopt phase 2 in both spin states. Comparison of 1-3 reveals that the more cooperative spin transition in 1, and its separate crystallographic phase transition, can both be attributed to an intermolecular steric interaction involving the methylsulfanyl substituents. All three compounds exhibit the light-induced excited-spin-state trapping (LIESST) effect with T(LIESST=70-80 K), but show complicated LIESST relaxation kinetics involving both weakly cooperative (exponential) and strongly cooperative (sigmoidal) components.
dc.language.isoen
dc.publisherWiley-VCH Verlag
dc.subject.encrystal engineering
dc.subject.eniron
dc.subject.enN‐ligands
dc.subject.enphotomagnetic properties
dc.subject.enspin crossover
dc.title.enDecoupled spin crossover and structural phase transition in a molecular iron(II) complex
dc.typeArticle de revue
dc.identifier.doi10.1002/chem.201406307
dc.subject.halChimie/Chimie de coordination
bordeaux.journalChemistry - A European Journal
bordeaux.page4805-4816
bordeaux.volume21
bordeaux.issue12
bordeaux.peerReviewedoui
hal.identifierhal-01128451
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01128451v1
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