Investigation of Charge-Ordered Barium Iron Fluorides with One-Dimensional Structural Diversity and Complex Magnetic Interactions

Three mixed-valence barium iron fluorides, Ba7Fe7F34, Ba2Fe2F9, and BaFe2F7, were prepared through hydrothermal redox reactions. The characteristic structures of these compounds feature diverse distributions of FeIIF6 octahedra and FeIIIF6 groups. Ba7Fe7F34 contained one-dimensional infinite ∞[FeIIFeIII 6F34]14– double chains, comprising cis corner-sharing octahedra along the b direction; Ba2Fe2F9 contained one-dimensional ∞[Fe2F9]4– double chains, consisting of cis corner-sharing octahedra along the chain (a-axis direction) and trans corner-sharing octahedra vertical to the chain, while BaFe2F7 revealed three-dimensional (3D) frameworks that consist of isolated edge-sharing dinuclear FeII 2F10 units linked via corners by FeIIIF6 octahedra. Magnetization and Mössbauer spectroscopy measurements revealed that Ba7Fe7F34 exhibits an antiferromagnetic phase transition at ∼11 K, where ferrimagnetic ∞[FeIIFeIII 6F34]14– double chains are arranged in a paralleling manner, while Ba2Fe2F9 shows canted antiferromagnetic ordering at ∼32.5 K, leading to noncollinear spin ordering.