EPR study of monomeric and dimeric vanadyl ions in SbVO 5

A new compound, SbVO 5 , formed in the V-Sb-O system, has been synthesized and investigated using the electron paramagnetic resonance (EPR) technique. SbVO 5 has been prepared by two methods: by heating equimolar mixtures of V 2 O 5 and f -Sb 2 O 4 in air and by oxidation of the known phase (SbVO 4.5 ) of rutile type obtained in pure argon at temperatures between 550 v C and 650 v C. At room temperature only a weak EPR signal from the powder sample of SbVO 5 was detected corroborating the absence of bulk V(IV) ions in the structure. Comparison with the CuSO 4 reference sample revealed that only 0.02% vanadium ions are EPR active. Intense EPR spectra obtained in the low temperature range, below 100 v K, showed a well resolved hyperfine structure typical of isolated vanadium ions in axial symmetry, present as VO 2+ species, and a broad line attributed to V 4+ -O-V 5+ bonds. The hyperfine structure lines could be analyzed by an axial spin Hamiltonian with g =1.9311, g =1.9425 and A =181 ‐ 10 m 4 v cm m 1 , A =54 ‐ 10 m 4 v cm m 1 . The spectrum recorded at the lowest obtainable temperature T=3.65 v K contains yet another component which is typical of a triplet state indicating the presence of two interacting VO 2+ nuclei with spin 1/2 giving a singlet S=0 and a triplet S=1 state. The appearance of a low-field line (B∼1600 v Gs at g , 4) is another diagnostic for the presence of dimeric species and is attributed to the forbidden j M S = - 2 transition.