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Solvate-dependent spin crossover and exchange in cobalt(II) oxazolidine nitroxide chelates

hal.structure.identifierSchool of Chemistry
hal.structure.identifierSchool of Pharmacy and Biomolecular Sciences
dc.contributor.authorGASS, Ian A.
hal.structure.identifierDepartment of Chemistry [Mumbai]
dc.contributor.authorTEWARY, Subrata
hal.structure.identifierDepartment of Chemistry [Mumbai]
dc.contributor.authorRAJARAMAN, Gopalan
hal.structure.identifierSchool of Chemistry
dc.contributor.authorASADI, Mousa
hal.structure.identifierSchool of Chemistry
dc.contributor.authorLUPTON, David W.
hal.structure.identifierSchool of Chemistry
dc.contributor.authorMOUBARAKI, Boujemaa
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorCHASTANET, Guillaume
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorLÉTARD, Jean-Francois
hal.structure.identifierSchool of Chemistry
dc.contributor.authorMURRAY, Keith S.
dc.date.issued2014-05-19
dc.identifier.issn0020-1669
dc.description.abstractEnTwo oxazolidine nitroxide complexes of cobalt(II), [Co(II)(L(*))2](B(C6F5)4)2*CH2Cl2 (1) and [Co(II)(L(*))2](B(C6F5)4)2*2Et2O (2), where, L(*) is the tridentate chelator 4,4-dimethyl-2,2-bis(2-pyridyl)oxazolidine N-oxide, have been investigated by crystallographic, magnetic, reflectivity, and theoretical (DFT) methods. This work follows on from a related study on [Co(II)(L(*))2](NO3)2 (3), a multifunctional complex that simultaneously displays magnetic exchange, spin crossover, and single molecule magnetic features. Changing the anion and the nature of solvation in the present crystalline species leads to significant differences, not only between 1 and 2 but also in comparison to 3. Structural data at 123 and 273 K, in combination with magnetic data, show that at lower temperatures 1 displays low-spin Co(II)-to-radical exchange with differences in fitted J values in comparison to DFT (broken symmetry) calculated J values ascribed to the sensitive influence of a tilt angle (θ) formed between the Co(dz(2)) and the trans-oriented O atoms of the NO radical moieties in L(*). Spin crossover in 1 is evident at higher temperatures, probably influenced by the solvate molecules and crystal packing arrangement. Complex 2 remains in the high-spin Co(II) state between 2 and 350 K and undergoes antiferromagnetic exchange between Co-radical and radical-radical centers, but it is difficult to quantify. Calculations of the magnetic orbitals, eigenvalue plots, and the spin densities at the Co and radical sites in 1 and 2 have yielded satisfying details on the mechanism of metal-radical and radical-radical exchange, the radical spins being in π*NO orbitals.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enSolvate-dependent spin crossover and exchange in cobalt(II) oxazolidine nitroxide chelates
dc.typeArticle de revue
dc.identifier.doi10.1021/ic5001057
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page5055-5066
bordeaux.volume53
bordeaux.issue10
bordeaux.peerReviewedoui
hal.identifierhal-01015120
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01015120v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Inorganic%20Chemistry&rft.date=2014-05-19&rft.volume=53&rft.issue=10&rft.spage=5055-5066&rft.epage=5055-5066&rft.eissn=0020-1669&rft.issn=0020-1669&rft.au=GASS,%20Ian%20A.&TEWARY,%20Subrata&RAJARAMAN,%20Gopalan&ASADI,%20Mousa&LUPTON,%20David%20W.&rft.genre=article


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