Electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD) and EPR detected via MCD (MCD-EPR) investigations have been performed on rare-earth activated oxyfluoride glasses and glass-ceramics. Er³⁺, Gd³⁺, and Mn²⁺ activators in oxyfluoride glass-ceramics show paramagnetic MCD behaviour and the MCD-EPR has been detected. The results of the MCD-EPR measurements for the Er-doped oxyfluoride glass-ceramics showed that Er³⁺ ions in the CaF₂ crystallites in these ceramics embed only in the cubic symmetry environment, similarly to the previous observations of cubic Gd³⁺ centres in the glass-ceramics containing CaF₂. Finally, the correlation of optics and paramagnetic centres is discussed for Mn-doped YAlO₃ ceramics.
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