Anionic ordering is a promising route to engineer physical properties in functional heteroanionic materials. A central challenge in the study of anion-ordered compounds lies in developing robust synthetic strategies to control anion occupation and in understanding the resultant implications for electronic structure. Here, we show that epitaxial strain induces preferential occupation of F and O on the anion sites in perovskite oxyfluoride SrMnO2.5-dFg films grown on different substrates. Under compressive strain, F tends to take the apical-like sites, which was revealed by F and O K-edge linearly polarized x-ray absorption spectroscopy and density functional theory calculations, resulting in an enhanced c-axis expansion. Under tensile strain, F tends to take the equatorial-like sites, enabling the longer Mn-F bonds to lie within the plane. The anion ordered oxyfluoride films exhibit a significant orbital polarization of the 3d electrons, distinct F-site dependence to their valence band density of states, and an enhanced resistivity when F occupies the apical-like anion site compared to the equatorial-like site. By demonstrating a general strategy for inducing anion-site order in oxyfluoride perovskites, this work lays the foundation for future materials design and synthesis efforts that leverage this greater degree of atomic control to realize new polar or quasi-two-dimensional materials.
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