Mixed anion compounds in the Fm3̅m vacancy ordered perovskite structure were synthesized and characterized experimentally and computationally with a focus on compounds where A = Cs⁺. Pure anion Cs₂SnX₆ compounds were formed with X = Cl, Br, and I using a room temperature solution phase method. Mixed anion compounds were formed as solid solutions of Cs₂SnCl₆ and Cs₂SnBr₆ and a second series from Cs₂SnBr₆ and Cs₂SnI₆. Single phase structures formed across the entirety of both composition series with no evidence of long-range anion ordering observed by diffraction. A distortion of the cubic A₂BX₆ structure was identified in which the spacing of the BX₆ octahedra changes to accommodate the A site cation without reduction of overall symmetry. Optical band gap values varied with anion composition between 4.89 eV in Cs₂SnCl₆ to 1.35 eV in Cs₂SnI₆ but proved highly nonlinear with changes in composition. In mixed halide compounds, it was found that lower energy optical transitions appeared that were not present in the pure halide compounds, and this was attributed to lowering of the local symmetry within the tin halide octahedra. The electronic structure was characterized by photoemission spectroscopy, and Raman spectroscopy revealed vibrational modes in the mixed halide compounds that could be assigned to particular mixed halide octahedra. This analysis was used to determine the distribution of octahedra types in mixed anion compounds, which was found to be consistent with a near-random distribution of halide anions throughout the structure, although some deviations from random halide distribution were noted in mixed iodide-bromide compounds, where the larger iodide anions preferentially adopted trans configurations.

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