Barium imidonitridophosphate BaP 6 N 10 NH was synthesized at 5GPa and 1000 8Cw ith ah igh-pressureh ightemperature approach using the multianvil technique. Ba(N 3 ) 2 ,P 3 N 5 and NH 4 Cl were used as starting materials, applying ac ombination of azide and mineralizer routes.T he structure elucidationo fB aP 6 N 10 NH (P6 3 , a = 7.5633(11), c = 8.512(2) , Z = 2) was performed by ac ombination of transmission electron microscopy and single-crystal diffraction with microfocused synchrotron radiation. Phase purity was verifiedb yR ietveld refinement. 1 Ha nd 31 Ps olid-state NMR and FTIR spectroscopy are consistentw ith the structure model.T he chemical composition was confirmed by energydispersive X-ray spectroscopy and CHNS analyses. Eu 2 + -dopeds amples of BaP 6 N 10 NH show blue emission upon excitationw ith UV to blue light (l em = 460 nm, fwhm = 2423 cm À1 )r epresenting unprecedentedE u 2 + -luminescence of an imidonitride.problem can be resolved with high-pressure high-temperature syntheses according to the principle of Le Chatelier.D espite their challenging syntheses, the structuralc hemistryo fn itridophosphates is intriguing, as they can reach even higher degrees of condensation (i.e.,atomicratio k of tetrahedra centers and ligands) than oxosilicates (k(P 3 N 5 ) = 0.6, k(SiO 2 ) = 0.5). [2][3][4][5][6][7][8] Thus, nitridophosphates feature triply-bridging N [3] atoms or even edge-sharing PN 4 tetrahedra. [9] Moreover,n itridophosphates have recently been investigated as host materials for Eu 2 + -doped phosphors. [10][11][12] Although the number of nitridophosphate-based phosphors is still limited, the known examples almostc over the entire visible spectrum. For example, MP 2 N 4 :Eu 2 + (M = Ca, Sr,B a) showse missions from 450 to 570 nm, featuring full width at half-maximum (fwhm) values comparable to established nitride-based phosphorm aterials. [10] Furthermore, Eu 2 + -doped quaternary zeolite-like nitridophosphates Ba 3 P 5 N 10 X (X = Cl, Br,I )h aveb een investigated concerning their luminescence properties. [11,12] Ba 3 P 5 N 10 Br,f or example, has been discussed as an atural-white-light single emitter. [12] In contrast, quaternary imidonitridophosphates, which have been discussed as possible intermediates on ther eactionp athway to highly condensed nitridophosphates, are completely unexplored concerningt heir luminescence properties. [8] These H-containing compounds can be synthesized using starting materials like amides, NH 4 Cl, or the underlying ternary imide nitrideH PN 2 . [13][14][15][16][17] For years, only the less condensed alkali metal amide/imide compounds Cs 5 P(NH) 4 (NH 2 ) 2 , Rb 8 [P 4 N 6 (NH) 4 ](NH 2 ) 2 andN a 10 [P 4 N 4 (NH) 6 ](NH 2 ) 6 (NH 3 ) 0.5 have been known,s howing discrete tetrahedra and adamantane-like [P 4 N 10Àx (NH) x ] (10Àx)À cages, respectively. [13][14][15] The highly condensed alkaline earth metal imidonitridophosphates MH 4 P 6 N 12 (M = Mg, Ca, Sr) were the first representativess howing layered network structure types. [8,17] In framework-type SrP...
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The recently introduced nitridophosphate synthesis in a hot isostatic press (HIP) enabled simple access to large‐scale product quantities starting from exclusively commercially available starting materials. Herein, we show that this method is suitable for the synthesis of highly condensed functional nitridophosphates, as well. Hence, the syntheses of the nitridophosphate zeolites Ba3P5N10X (X=Cl, Br) are presented as proof of concept for this innovative access. Furthermore, samples of unprecedented Sr3P5N10X (X=Cl, Br) were prepared and characterized to demonstrate the advantages of this synthetic approach over commonly used methods. Luminescence investigations on Eu2+‐doped samples of AE3P5N10X (AE=Sr, Ba; X=Cl, Br) were carried out and characteristics of observed emission bands are discussed.
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