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X-ray absorption spectroscopy, Ruthenates, Ruthenium, Valence states, Crystal structure
Abstract:
Single crystals of the quaternary R-type ferrites BaLiRu5O11 [a = 11.628(6) Å, c = 13.7596(5) Å], and BaCu1+xRu5–xO11 [a = 11.6825(6) Å, c = 13.8051(7) Å], and their quinary solid solution BaLi1–xCux+δRu5–δO11 [a = 11.6453(2) Å, c = 13.7772(3) Å] were obtained by flux growth technique. X-ray diffraction reveals the compounds to crystallize in space group P63/m with Z = 8. Measurements of the magnetic susceptibility of BaLiRu5O11 and BaCu1+xRu5–xO11, applying Curie–Weiss fits, confirm their paramagnetic behavior with temperature independent contributions of χ0,mol = 3.27 × 10–3 cm3·mol–1 and χ0,mol = 2.47 × 10–3 cm3·mol–1, respectively. Furthermore, the valence state of Ru in BaLiRu5O11 and BaCu1+xRu5–xO11 was determined to +3.8 by X-ray absorption spectroscopy. Cu in BaCu1+xRu5–xO11 is dominating in a +2 state according to X-ray photoelectron and X-ray absorption spectroscopy, while a minor amount in +1 state may represent the excess copper substituting some Ru within a distorted Kagome net arrangement.
