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Thermal- and Light-Induced Spin-Crossover Bistability in a Disrupted Hofmann-Type 3D Framework.

hal.structure.identifierSchool of Chemistry
dc.contributor.authorSCIORTINO, Natasha F.
hal.structure.identifierSchool of Chemistry
dc.contributor.authorNEVILLE, Suzanne M.
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorLÉTARD, Jean-François
hal.structure.identifierSchool of Chemistry
dc.contributor.authorMOUBARAKI, Boujemaa
hal.structure.identifierSchool of Chemistry
dc.contributor.authorMURRAY, Keith S.
hal.structure.identifierSchool of Chemistry
dc.contributor.authorKEPERT, Cameron J.
dc.date.issued2014
dc.identifier.issn0020-1669
dc.description.abstractEnThe expected 3D and 2D topologies resulting from combining approximately linear bis- or monopyridyl ligands with [Fe(II)M(II)(CN)4] (M(II) = Pt, Pd, Ni) 4,4-grid sheets are well established. We show here the magnetic and structural consequences of incorporating a bent bispyridyl linker ligand in combination with [Fe(II)Pt(II)(CN)4] to form the material [Fe(H2O)2Fe(DPSe)2(Pt(CN)4)2]*3EtOH (DPSe = 4,4'-dipyridylselenide). Structural investigations reveal an unusual connectivity loosely resembling a 3D Hofmann topology where (1) there are two distinct local iron(II) environments, [Fe(II)N6] (Fe1) and [Fe(II)N4O2] (Fe2), (2) as a consequence of axial water coordination to Fe2, there are "holes" in the [Fe(II)Pt(II)(CN)4] 4,4 sheets because of some of the cyanido ligands being terminal rather than bridging, and (3) bridging of adjacent sheets occurs only through one in two DPSe ligands, with the other acting as a terminal ligand binding through only one pyridyl group. The magnetic properties are defined by this unusual topology such that only Fe1 is in the appropriate environment for a high-spin to low-spin transition to occur. Magnetic susceptibility data reveal a complete and abrupt hysteretic spin transition (T1/2↓ = 120 K and T1/2↑ = 130 K) of this iron(II) site; Fe2 remains high-spin. This material additionally exhibits a photomagnetic response (uncommon for Hofmann-related materials), showing light-induced excited spin-state trapping [LIESST; T(LIESST) = 61 K] with associated bistability evidenced in a hysteresis loop (T1/2↓ = 60 K and T1/2↑ = 66 K).
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enThermal- and Light-Induced Spin-Crossover Bistability in a Disrupted Hofmann-Type 3D Framework.
dc.typeArticle de revue
dc.identifier.doi10.1021/ic500323r
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page7886-7893
bordeaux.volume53
bordeaux.issue15
bordeaux.peerReviewedoui
hal.identifierhal-01064666
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01064666v1
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