Discrepancy between the spin distribution and the magnetic ground state for a triaminoxyl substituted triphenylphosphine oxide derivative.
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | BENEDI BOROBIA, Oscar | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | GUIONNEAU, Philippe | |
hal.structure.identifier | Max Planck Institute for Biophysical Chemistry [MPI-BPC] | |
hal.structure.identifier | Anorganisch-chemisches Institut | |
dc.contributor.author | HEISE, Henrike | |
hal.structure.identifier | Anorganisch-chemisches Institut | |
dc.contributor.author | FRANK H., Köhler | |
hal.structure.identifier | Laboratoire de Physico-Chimie Moléculaire [LPCM] | |
dc.contributor.author | DUCASSE, Laurent | |
hal.structure.identifier | Institut de Ciència de Materials de Barcelona [ICMAB] | |
dc.contributor.author | VIDAL-GANCEDO, Jose | |
hal.structure.identifier | Institut de Ciència de Materials de Barcelona [ICMAB] | |
dc.contributor.author | VECIANA, Jaume | |
hal.structure.identifier | Laboratoire de Chimie du solide et inorganique moléculaire [LCSIM] | |
dc.contributor.author | GOLHEN, Stéphane | |
hal.structure.identifier | Organométalliques: Matériaux et Catalyse | |
dc.contributor.author | OUAHAB, Lahcène | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
hal.structure.identifier | Laboratoire de chimie de coordination [LCC] | |
dc.contributor.author | SUTTER, Jean-Pascal | |
dc.date.issued | 2005 | |
dc.identifier.issn | 0947-6539 | |
dc.description.abstractEn | The 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.iso | en | |
dc.publisher | Wiley-VCH Verlag | |
dc.subject.en | EPR spectroscopy | |
dc.subject.en | magnetic properties | |
dc.subject.en | NMR spectroscopy | |
dc.subject.en | radicals | |
dc.subject.en | spin distribution | |
dc.title.en | Discrepancy between the spin distribution and the magnetic ground state for a triaminoxyl substituted triphenylphosphine oxide derivative. | |
dc.type | Article de revue | |
dc.identifier.doi | 10.1002/chem.200400656 | |
dc.subject.hal | Chimie/Matériaux | |
bordeaux.journal | Chemistry - A European Journal | |
bordeaux.page | p. 128-139 | |
bordeaux.volume | vol. 11, n° 1 | |
bordeaux.peerReviewed | oui | |
hal.identifier | hal-00021157 | |
hal.version | 1 | |
hal.popular | non | |
hal.audience | Non spécifiée | |
hal.origin.link | https://hal.archives-ouvertes.fr//hal-00021157v1 | |
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