The solid solution series NaMgH3 amp; 8722;xFx x 0, 0.5, 1, 1.5, 2, 2.5, 3 was synthesized by solid state reactions under hydrogen gas pressure from binary ionic hydrides, fluorides and magnesium. Rietveld refinement based on Xray powder diffraction data revealed the GdFeO3 structure type for all compounds and a trend of lattice parameters according to Vegard s law. The anion distribution in NaMgD2F and NaMgD1.5F1.5 was found to be statistical by Rietveld refinement based on neutron powder diffraction data. Photoluminescence measurements on europium II substituted NaMgH3 amp; 8722;xFx revealed a strong red shift of the emission wavelength amp; 955;em 665 nm for NaMgH2F Eu in comparison to violet emitting NaMgF3 E
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