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

Möncke, Doris; Kamitsos, E. I.; Herrmann, Andreas; Ehrt, D.; Friedrich, M.

doi:10.1016/j.jnoncrysol.2011.02.017

Cited by 73 publications

(60 citation statements)

References 31 publications

(171 reference statements)

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“…This resonance arises from the magnetic dipolar transition at the 6 S 5/2 ground state of Mn 2+ . 15,16,27,28 The sextet hyperfine structure reported for low Mn concentrations 11,16,[28][29][30] is not seen in any of the SP glasses studied here. The hyperfine structure, which arises from isolated Mn 2+ ions, disappears with the development of Mn 2+ -Mn 2+ magnetic interactions.…”

Section: Electron Paramagnetic Resonance Spectroscopymentioning

confidence: 79%

“…A peak maximum at 657 nm, as seen for the 5Mn glass, is indicative for an octahedral coordination of Mn 2+ ions in the glass structure. [15][16][17]24 The total absence of luminescence at 525 nm, which would correspond to tetrahedrally coordinated Mn 2+ ions, 15,16,23,24 shows that all Mn ions are 6-fold coordinated in the studied SP glasses.…”

Section: B Luminescence Spectroscopymentioning

confidence: 93%

“…For example in phosphate glasses, different Mn 2+ /Mn 3+ ratios were observed depending on glass composition, the melting conditions or the melting atmosphere. [16][17][18][19] According to the Lambert-Beer law,…”

Section: A Absorption Spectroscopymentioning

confidence: 99%

“…The latter phenomenon is wellknown and is ascribed to the enhancement of Mn 2+ -Mn 2+ interactions, for example, due to clustering effects. 11,16,24 Furthermore, the position of the emission peak strongly depends on the Mn 2+ environment. A peak maximum at 657 nm, as seen for the 5Mn glass, is indicative for an octahedral coordination of Mn 2+ ions in the glass structure.…”

Section: B Luminescence Spectroscopymentioning

confidence: 99%

“…11 However, in borate and borosilicate glasses the opposite effect was witnessed in the form of exchange narrowing. 16,27,28,31,32 With increasing Mn ion content, edge-sharing MnO 6 octahedra are formed for which the Mn 2+ -Mn 2+ distances are around 3 Å instead of the 4 Å observed in corner-sharing octahedra. The resulting stronger magnetic interactions lead to a narrowing of the EPR resonance, which is also seen in Figure 4 for SP glasses with high Mn levels.…”

Section: Electron Paramagnetic Resonance Spectroscopymentioning

confidence: 99%

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Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses

Möncke

Sirotkin

Stavrou

et al. 2014

The Journal of Chemical Physics

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Ionic sulfophosphate liquids of the type ZnO-Na2O-Na2SO4-P2O5 exhibit surprising glass forming ability, even at slow or moderate cooling rate. As a concept, they also provide high solubility of transition metal ions which could act as cross-linking sites between the sulfate and phosphate entities. It is therefore investigated how the replacement of ZnO by MnO and/or FeO affects the glass structure and the glass properties. Increasing manganese levels are found to result in a monotonic increase of the transition temperature Tg and most of the mechanical properties. This trend is attributed to the change of metal-ion coordination from four-fold around Zn(2+) to six-fold around Mn(2+) ions. The higher coordination facilitates cross-linking of the ionic structural entities and subsequently increases Tg. Raman and infrared spectroscopy show that the structure of these glasses involves only SO4(2-) and PO4 (3-) monomers as well as P2O7(4-) dimers. Replacement of ZnO by MnO is found to favour PO4(3-) over P2O7(4-) species, a trend which is enhanced by co-doping with FeO. Both transition metal ions show, like Zn(2+), a preference to selectively coordinate to phosphate anionic species, as opposed to sodium ions which coordinate mainly to sulfate anions. EPR spectroscopy finally shows that divalent Mn(2+) ions are present primarily in MnO6-clusters, which, in the studied sulfophosphate glasses, convert upon increasing MnO content from corner-sharing to edge-sharing entities.

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Section: Electron Paramagnetic Resonance Spectroscopymentioning

confidence: 79%

Section: B Luminescence Spectroscopymentioning

confidence: 93%

Section: A Absorption Spectroscopymentioning

confidence: 99%

Section: B Luminescence Spectroscopymentioning

confidence: 99%

Section: Electron Paramagnetic Resonance Spectroscopymentioning

confidence: 99%

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Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses

Möncke

Sirotkin

Stavrou

et al. 2014

The Journal of Chemical Physics

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⁹Be and ³¹P NMR analyses on the influence of imino groups on Be²⁺ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions

Maki

Tsujito

Nariai

et al. 2013

Magnetic Reson in Chemistry

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The complexation behaviors of Be²⁺ with cyclo-μ-imido triphosphate anions, cP₃O₉-n(NH)n(3-)n= 1, 2),have been investigated by both ⁹Be and ³¹P NMR techniques at -2.3 °C in order to clarify the coordination structures of the complexes. The spectra showed that cP₃O₉n(NH)n (n = 1, 2) ligands form ML, ML₂, and M₂L complexes with Be²⁺ ions, and the formation of complexes coordinating with nitrogen atoms of the cyclic framework in the ligand molecule has been excluded. These complexation trends are very similar to those of Be²⁺-cP₃O₆(NH)⁻³₃system, which has been reported by us. The peak deconvolution of ⁹BeNMR spectra made these beryllium complexes amenable to stability constant determinations. The stability constants of the complexes increase with an increase in the protonation constants of the ligands as the number of imino groups, which constitute the ligand molecules, is ascended. This increase is primarily attributable to the lower electronegativity of nitrogen atoms than oxygen atoms, which are directly bonded to central phosphorus atoms; moreover, tautomerism equilibrium in the entire of the imidopolyphosphate molecule is also responsible to the higher basicity. ³¹P NMR spectra measured concurrently have verified the formation of the complexes estimated by the ⁹Be NMR measurement. Intrinsic ³¹P NMR chemical shift values of the phosphorus atoms belonging to ligand molecules complexed with Be²⁺ cations have been determined. Not only the protonation constants but also the stability constants of all Be²⁺ complexes increase approximately linearly with an increase in the number of imino groups.

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Optical and EPR studies of zinc phosphate glasses containing Mn2+ ions

et al. 2020

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

Cited by 73 publications

References 31 publications

Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses

Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses

⁹Be and ³¹P NMR analyses on the influence of imino groups on Be²⁺ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions

Optical and EPR studies of zinc phosphate glasses containing Mn2+ ions

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

Cited by 73 publications

References 31 publications

Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses

Partitioning and structural role of Mn and Fe ions in ionic sulfophosphate glasses

9Be and 31P NMR analyses on the influence of imino groups on Be2+ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions

Optical and EPR studies of zinc phosphate glasses containing Mn2+ ions

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⁹Be and ³¹P NMR analyses on the influence of imino groups on Be²⁺ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions