Bonding and ion–ion interactions of Mn2+ ions in fluoride-phosphate and boro-silicate glasses probed by EPR and fluorescence spectroscopy

Electron paramagnetic resonance (EPR) and fluorescence spectroscopy are sensitive and selective methods for probing coordination and bonding of Mn2+ ions in glasses. Both methods provide additional information on Mn–Mn ion interactions and cluster formation. Mn2+ was found to be tetrahedrally coordinated in boro-silicate glasses of high optical basicity, and octahedrally coordinated in low alkaline boro-silicate glasses (duran-type) as in fluoride-phosphate glasses. Broad emission bands and multicomponent fluorescence decay curves in duran glasses indicate very strong Mn–Mn ion interactions and the presence of multiple Mn2+ sites. Site distribution is more homogenous in metaphosphate glasses, though concentration quenching is apparent at high Mn-levels. As the Mn-content increases the EPR spectra show exchange narrowing due to a decrease in the Mn–Mn distances in the duran series, but show extreme linewidth broadening due to increased cluster sizes at constant Mn–Mn distances for metaphosphate glasses. For the fluoride-phosphate and boro-silicate systems investigated, fluorescence lifetimes are found to decrease as the wavelength of the emission maximum increases and with increasing g-values of the sextet at g = 2. For octahedral coordination of Mn2+ ions the EPR hyperfine splitting constant decreases linearly with increasing optical basicity, as a result of an increasing covalent character of the Mn2+–ligand bond.