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Discrepancy between the spin distribution and the magnetic ground state for a triaminoxyl substituted triphenylphosphine oxide derivative.

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorBENEDI BOROBIA, Oscar
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorGUIONNEAU, Philippe
hal.structure.identifierMax Planck Institute for Biophysical Chemistry [MPI-BPC]
hal.structure.identifierAnorganisch-chemisches Institut
dc.contributor.authorHEISE, Henrike
hal.structure.identifierAnorganisch-chemisches Institut
dc.contributor.authorFRANK H., Köhler
hal.structure.identifierLaboratoire de Physico-Chimie Moléculaire [LPCM]
dc.contributor.authorDUCASSE, Laurent
hal.structure.identifierInstitut de Ciència de Materials de Barcelona [ICMAB]
dc.contributor.authorVIDAL-GANCEDO, Jose
hal.structure.identifierInstitut de Ciència de Materials de Barcelona [ICMAB]
dc.contributor.authorVECIANA, Jaume
hal.structure.identifierLaboratoire de Chimie du solide et inorganique moléculaire [LCSIM]
dc.contributor.authorGOLHEN, Stéphane
hal.structure.identifierOrganométalliques: Matériaux et Catalyse
dc.contributor.authorOUAHAB, Lahcène
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierLaboratoire de chimie de coordination [LCC]
dc.contributor.authorSUTTER, Jean-Pascal
dc.date.issued2005
dc.identifier.issn0947-6539
dc.description.abstractEnThe magnetic interaction and spin transfer via phosphorus have been investigated for the tri-tert-butylaminoxyl para-substituted triphenylphosphine oxide. For this radical unit, the conjugation existing between the * orbital of the NO group and the phenyl orbitals leads to an efficient delocalization of the spin from the radical to the neighboring aromatic ring. This has been confirmed by using fluid solution high-resolution EPR and solid state MAS NMR spectroscopy. The spin densities located on the atoms of the molecule could be probed since 1H, 13C, 14N, and 31P are nuclei active in NMR and EPR, and lead to a precise spin distribution map for the triradical. The experimental investigations were completed by a DFT computational study. These techniques established in particular that spin density is located at the phosphorus (=-15×10-3 au), that its sign is in line with the sign alternation principle and that its magnitude is in the order of that found on the aromatic C atoms of the molecule. Surprisingly, whereas the spin distribution scheme supports ferromagnetic interactions among the radical units, the magnetic behavior found for this molecule revealed a low-spin ground state characterized by an intramolecular exchange parameter of J=-7.55 cm-1 as revealed by solid state susceptibility studies and low temperature EPR. The X-ray crystal structures solved at 293 and 30 K show the occurrence of a crystallographic transition resulting in an ordering of the molecular units at low temperature.
dc.language.isoen
dc.publisherWiley-VCH Verlag
dc.subject.enEPR spectroscopy
dc.subject.enmagnetic properties
dc.subject.enNMR spectroscopy
dc.subject.enradicals
dc.subject.enspin distribution
dc.title.enDiscrepancy between the spin distribution and the magnetic ground state for a triaminoxyl substituted triphenylphosphine oxide derivative.
dc.typeArticle de revue
dc.identifier.doi10.1002/chem.200400656
dc.subject.halChimie/Matériaux
bordeaux.journalChemistry - A European Journal
bordeaux.pagep. 128-139
bordeaux.volumevol. 11, n° 1
bordeaux.peerReviewedoui
hal.identifierhal-00021157
hal.version1
hal.popularnon
hal.audienceNon spécifiée
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00021157v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemistry%20-%20A%20European%20Journal&rft.date=2005&rft.volume=vol.%2011,%20n%C2%B0%201&rft.spage=p.%20128-139&rft.epage=p.%20128-139&rft.eissn=0947-6539&rft.issn=0947-6539&rft.au=BENEDI%20BOROBIA,%20Oscar&GUIONNEAU,%20Philippe&HEISE,%20Henrike&FRANK%20H.,%20K%C3%B6hler&DUCASSE,%20Laurent&rft.genre=article


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