[CpNi(diselenolene)] neutral radical complexes: electron paramagnetic resonance and density functional theory investigations. - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry A Année : 2008

[CpNi(diselenolene)] neutral radical complexes: electron paramagnetic resonance and density functional theory investigations.

Résumé

77Se-enriched CpNi(bds) (bds = 1,2-benzenediselenolate), has been synthesized and its g tensor and 77Se hyperfine tensors have been obtained from its frozen solution electron paramagnetic resonance (EPR) spectrum. These parameters are consistent with those calculated by density functional theory (DFT); it is shown that 10% of the spin is localized on each selenium and that the direction associated to the maximum 77Se couplings is aligned along the gmin direction, perpendicular to the Ni(bds) plane. EPR measurements and DFT calculations are also carried out on the 77Se enriched complex CpNi(dsit) as well on the two dithiolene analogues CpNi(bdt) and CpNi(dmit). The optimized structures of the isolated CpNi(bds) and CpNi(bdt) complexes have been used to generate the idealized dimers (bds)NiCp...CpNi(bds) and (bdt)NiCp...CpNi(bdt) characterized by Cp...Cp overlap. The exchange parameters J calculated at the DFT level for these systems are in reasonable accord with the experimental values. The influence of the geometry of the dimer on its magnetic properties is assessed by calculating the variation of J as a function of the relative orientation of the two Ni(diselenolene) or Ni(dithiolene) planes.

Domaines

Autre

Dates et versions

hal-00283560 , version 1 (30-05-2008)

Identifiants

Citer

Philippe Grosshans, Prashant Adkine, Helena Sidorenkova, Mitsushiro Nomura, Marc Fourmigué, et al.. [CpNi(diselenolene)] neutral radical complexes: electron paramagnetic resonance and density functional theory investigations.. Journal of Physical Chemistry A, 2008, 112 (17), pp.4067-73. ⟨10.1021/jp800584v⟩. ⟨hal-00283560⟩
85 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More