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Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V1-xMox)2-δO3. The oxidation effects were monitored from the rate of paramagnetic V4+ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000°C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V4+ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V4+ content. [Copyright &y& Elsevier]

The crystal structure of new molybdenum-doped vanadium sesquioxides (V1−xMox)2O3 (0⩽x⩽0.20) has been studied at low temperature (10 K) and up to room temperature, through neutron and X-ray powder diffraction. The transition from insulating I- to metallic M-type phases, either by doping or thermally driven, is accompanied by an abrupt decrease of all interatomic distances. Within each structural type however, at 10 K, the effect of doping is essentially the same as at room temperature: it increases cation–oxygen distances, and decreases cation–cation distances, making the cationic coordination octahedra more regular. Thermal effects differ for each phase type: all interatomic distances normally increase in the M-type phase (but with different octahedral modifications depending on doping), but they decrease or remain constant in the I-type phase. This produces an unusual negative thermal expansion coefficient up to 5% at low temperature for the doped compounds. [Copyright &y& Elsevier]