Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family

Oxidation states of transition metal cations in spinels-type oxides are sometimes extremely difficult to determine by conventional spectroscopic methods. One of the most complex cases occurs when there are different cations, each one with several possible oxidation states, as in the case of the magnetoresistant Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) spinel-type family. In this contribution we describe the determination of the oxidation state of manganese and vanadium in Mn(2−x)V(1+x)O4 (x=0, 1/3,1) spinel-type compounds by analyzing XANES and high-resolution Kβ X-ray fluorescence spectra. The ionic models found are Mn2+2V4+O4, Mn2+5/3V3.5+4/3O4 and Mn2+V3+2O4. Combination of the present results with previous data provided a reliable cation distribution model. For these spinels, single magnetic electron paramagnetic resonance (EPR) lines are observed at 480 K showing the interaction among the different magnetic ions. The analysis of the EPR parameters show that g-values and relative intensities are highly influenced by the concentration and the high-spin state of Mn2+. EPR broadening linewidth is explained in terms of the bottleneck effect, which is due to the presence of the fast relaxing V3+ ion instead of the weak Mn2+ (S state) coupled to the lattice. The EPR results, at high temperature, are well explained assuming the oxidation states of the magnetic ions obtained by the other spectroscopic techniques. - Graphical abstract: View of the crystallographic structure of a spinel. It shows as an example one of the models of ion distribution determined for the spinels Mn(2−x)V(1+x)O4 (x=0, 1/3,1). Display Omitted - Highlights: • Determination of oxidation state of the metallic ions in Mn(2−x)V(1+x)O4 (x=0,1/3,1) by XAS and XES techniques. • The ionic models found are Mn2+2V4+O4, Mn2+5/3V3.5+4/3O4 and Mn2+V3+O4. • EPR spectra correspond almost exclusively to a resonance of Mn2+