Rafik Ballou | PubMed Health

PubMed2004

Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2).

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T = 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75 +/- 1% of one unpaired electron with an upper limit of 2.5%.

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PubMed2002

Analytical determination of the [Ln-aminoxyl radical] exchange interaction taking into account both the ligand-field effect and the spin-orbit coupling of the lanthanide ion (Ln = DyIII and HoIII).

Numerous compounds in which a paramagnetic LnIII ion is in an exchange interaction with a second spin carrier, such as a transition metal ion or an organic radical, have been described. However, except for GdIII, very little has been reported about the magnitude of the interactions. Indeed, for these ions both the ligand-field effects and the exchange interactions between the magnetic centers become relevant in the same temperature range; this makes the analysis of the magnetic behavior of such compounds more difficult. In this study, quantitative analyses of the thermal variations of the static isothermal initial magnetic susceptibility measured on powdered samples of the [Ln(NO3)3-[organic radical]2] (Ln = DyIII and HoIII) compounds were performed. The ligand-field effects on the Ln ions were taken into account, and the exchange interactions within a molecule were treated exactly within an appropriate Racah formalism. Values of the intramolecular [Ln-aminoxyl radical] exchange parameter have thus been rigorously deduced for both the Dy Kramers and Ho non-Kramers ion-based compounds. Ferromagnetic [Ln-radical] interactions are found for both the Dy and Ho derivatives with J = 8 cm(-1) and J = 4.5 cm(-1), respectively.

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