V. Ksenofontov

Spin Crossover in Fe(II) Molecular Compounds — Mössbauer and µSR Investigations

The compound [Fe(ptz)6](C104)2 (ptz = 1-propyl-tetrazole) displays a complete and gradual spin crossover centred around 125 K as evidenced by magnetic and muon measurements over the temperature range ∼ 4.2–300 K. Although the crystal structure reveals only one crystallographic site, line broadening is observed in the Mossbauer spectra in the vicinity of the spin transition. The muon spin relaxation behaviour of this compound indicates that a structural transformation rather than dynamic processes may account for the observed spectral features. Both the Mossbauer and muon measurements are consistent with a mixture of high and low spin Fe ions in the transition region.

Stoichiometry of LiNiO2 studied by Mössbauer spectroscopy

From the 61Ni and 57Fe Mossbauer spectroscopy data follows the cationic site assignment in Li1–x Ni1+x O2. Our data explain the ferromagnetic properties of this material because of the appearance of Ni2+ (S=1) among Ni3+ (S=1/2) in Ni3+O2 hexagonal planes. We have no evidence for the ferromagnetic interaction between the NiO2 layers through the excess Ni2+ ions substituting the Li+ ions. The presence of Ni2+ found in the Ni3+O2 planes explains the absence of the Jahn–Teller distortions probably because of the electronic transfer between the Ni3+ and Ni2+ ions.