Ammonothermal Synthesis of Ba2PO3N – An Oxonitridophosphate with Non‐Condensed PO3N Tetrahedra

The ortho‐oxonitridophosphate Ba2PO3N was synthesized under ammonobasic conditions (T = 1070 K, p = 120 MPa) in custom‐built high‐temperature autoclaves, starting from red phosphorus, BaO, NaN3 and KOH. Thus, single crystals of up to several hundred µm were obtained, which were used for single‐cryst...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2020-03, Vol.2020 (10), p.841-846
Main Authors: Wendl, Sebastian, Mallmann, Mathias, Strobel, Philipp, Schmidt, Peter J., Schnick, Wolfgang
Format: Article
Language:English
Subjects:
Ammonothermal synthesis
Autoclaves
Autoclaving
Barium oxides
Crystal structure
Crystals
Europium
Homology
Inorganic chemistry
Luminescence
Nitrides
Oxonitridophosphates
Potassium sulfate
Room temperature
Single crystals
Sodium azides
Spectrum analysis
Supercritical fluids
Tetrahedra
Ultraviolet radiation
X-ray diffraction
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Summary:The ortho‐oxonitridophosphate Ba2PO3N was synthesized under ammonobasic conditions (T = 1070 K, p = 120 MPa) in custom‐built high‐temperature autoclaves, starting from red phosphorus, BaO, NaN3 and KOH. Thus, single crystals of up to several hundred µm were obtained, which were used for single‐crystal X‐ray diffraction. Ba2PO3N [Pnma (no. 62), a = 7.596(2), b = 5.796(1), c = 10.212(3) Å, Z = 4] crystallizes in the β‐K2SO4 structure type with non‐condensed [PO3N]4– ions and is isotypic to its lighter homologues EA2PO3N (EA = Ca, Sr). Powder X‐ray diffraction, energy dispersive X‐ray and Fourier Transformed Infrared spectroscopy corroborate the crystal structure. The optical band gap was determined by means of diffuse reflectance UV/Vis spectroscopy to be 4.3 eV. Eu2+ doped samples show green luminescence (λem = 534 nm, fwhm = 85 nm/2961 cm–1) when irradiated with UV light (λexc = 420 nm). However, Ba2PO3N:Eu2+ shows strong thermal quenching, even at room temperature. The ammonothermal method was used for synthesis of the ortho‐oxonitridophosphate Ba2PO3N (T = 1070 K, p = 120 MPa) using custom‐built high‐temperature autoclaves. In doing so, crystallites with sizes up to several hundreds of µm could be obtained. Eu2+ doped samples show luminescence in the green region of the visible spectrum.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202000041