Mn⁴⁺-doped red-emitting fluorides are a promising class of materials for improving the color rendering and luminous efficiency of white light-emitting diodes (WLEDs). Phosphors based on hydrated cobalt hexafluoridometallates CoMF₆· 6H₂O (M = Si, Ge) activated with Mn⁴⁺ ions demonstrate red luminescence in the range of 600-650 nm upon excitation into the ^4A₂-^4T₂ (450-480 nm) and ^4A₂-^4T₁ (350-370 nm) bands. The luminescence spectra are formed by electron-phonon components at the ^2E-^4A₂ transition involving vibrations of the MnF₆^2- octahedron. The quantum yield of CoSiF₆· 6H₂O: Mn⁴⁺ is maximized at 357 nm excitation and is equal to 5% at 5.5% manganese concentration. When the crystal lattice of CoTiF₆· 6H₂O is formed, the depth of the potential minimum for the Mn⁴⁺ ion is smaller than in the case of CoSiF₆· 6H₂O and CoGeF₆·6H₂O, which leads to random fluctuations of the crystal field in the ensemble of positions occupied by this ion. Keywords: red phosphor, fluorides, Mn⁴⁺, Raman scattering, luminescence.

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