The isotypic nitridophosphates Ba 3 P 5 N 10 X (X = Cl, I) have been synthesized by high-temperature reaction under pressures between 1 and 5 GPa. The crystal structures of both compounds were solved and refined using single-crystal X-ray diffraction data. Accuracy of the structure determination as well as phase purity of the products were confirmed by Rietveld refinement and FTIR spectroscopy. The band gap values (4.0−4.3 eV) for the direct transitions were determined from UV−vis data using the Kubelka−Munk function and were confirmed by DFT calculations. Both compounds crystallize in the Ba 3 P 5 N 10 Br structure type (space group Pnma (No. 62), Z = 8; Ba 3 P 5 N 10 Cl, a = 12.5182(5) Å, b = 13.1798(5) Å, c = 13.7676(6) Å, R1 = 0.0214, wR2 = 0.0526; Ba 3 P 5 N 10 I, a = 12.6311(7) Å, b = 13.2565(8) Å, c = 13.8689(8) Å, R1 = 0.0257, wR2 = 0.0586) with a tetrahedra network being analogous to the topology of the JOZ zeolite structure type. The crystal structure is built up of all-side vertex-sharing PN 4 tetrahedra leading to a zeolite-like framework with three-dimensional achter-ring channels containing alternately Ba and respective halide atoms. The condensed dreier-, vierer-, and sechser-rings form two different composite building units made up of 3 4 4 2 8 6 -cages. Upon being doped with Eu 2+ , the title compounds exhibit intriguing luminescence properties, which were compared with that of Ba 3 P 5 N 10 Br:Eu 2+ . Upon excitation by near-UV light, nonsaturated color luminescence from multiple emission centers was observed in the orange (X = Cl) and cyan to amber (X = I) spectral range of the visible spectrum.

The (imido)nitridophosphates SrH P N and SrP N were synthesized as colorless crystals by high-pressure/high-temperature reactions using the multianvil technique (5 GPa, ca. 1075 °C). Stoichiometric amounts of Sr(N ) P N , and amorphous HPN were used as starting materials. Whereas the crystal structure of SrH P N was solved and refined from single-crystal X-ray diffraction data and confirmed by Rietveld refinement, the structure of SrP N was determined from powder diffraction data. In order to confirm the structures, H and P solid-state NMR spectroscopy and FTIR spectroscopy were carried out. The chemical composition was confirmed with EDX measurements. Both compounds show unprecedented layered network structure types, built up from all-side vertex-sharing PN tetrahedra which are structurally related. The structural comparison of both compounds gives first insights into the hitherto unknown condensation mechanism of nitridophosphates under high pressure.

The nitridophosphates AEP8N14 (AE=Ca, Sr, Ba) were synthesized at 4–5 GPa and 1050–1150 °C applying a 1000 t press with multianvil apparatus, following the azide route. The crystal structures of CaP8N14 and SrP8N14 are isotypic. The space group Cmcm was confirmed by powder X‐ray diffraction. The structure of BaP8N14 (space group Amm2) was elucidated by a combination of transmission electron microscopy and diffraction of microfocused synchrotron radiation. Phase purity was confirmed by Rietveld refinement. IR spectra are consistent with the structure models and the chemical compositions were confirmed by X‐ray spectroscopy. Luminescence properties of Eu2+‐doped samples were investigated upon excitation with UV to blue light. CaP8N14 (λem=470 nm; fwhm=1380 cm−1) and SrP8N14 (λem=440 nm; fwhm=1350 cm−1) can be classified as the first ultra‐narrow‐band blue‐emitting Eu2+‐doped nitridophosphates. BaP8N14 shows a notably broader blue emission (λem=417/457 nm; fwhm=2075/3550 cm−1).

Nitridophosphates are aw ell-studied class of compounds with high structural diversity.H owever,t heir synthesis is quite challenging, particularly due to the limited thermal stability of starting materials like P 3 N 5 .T ypically,i tr equires even high-pressuret echniques (e.g. multianvil) in most cases.H erein, we establish the ammonothermal method as av ersatile synthetic tool to access nitridophosphates with different degrees of condensation. a-Li 10 P 4 N 10 , b-Li 10 P 4 N 10 ,L i 18 P 6 N 16 ,C a 2 PN 3 ,S rP 8 N 14 ,a nd LiPN 2 were synthe-sized in supercritical NH 3 at temperatures and pressures up to 1070 Ka nd 200 MPa employing ammonobasic conditions. The products were analyzed by powder X-ray diffraction, energy dispersive X-ray spectroscopy,a nd FTIR spectroscopy. Moreover,w ee stablished red phosphorus as as tartingm aterial for nitridophosphate synthesis instead of commonly used and not readily availablep recursors, such as P 3 N 5 .T his opens ap romisingp reparativea ccess to the emerging compound class of nitridophosphates.

(Oxo)Nitridophosphates have recently been identified as a promising compound class for application in the field of solid‐state lighting. Especially, the latest medium‐pressure syntheses under ammonothermal conditions draw attention of the semiconductor and lighting industry on nitridophosphates. In this contribution, we introduce hot isostatic presses as a new type of medium‐pressure synthetic tool, further simplifying nitridophosphate synthesis. In a second step, phosphorus nitride was replaced as starting material by red phosphorus, enabling the synthesis of Ca2PN3 as model compound, starting only from readily available compounds. Moreover, first luminescence investigations on Eu2+‐doped samples reveal Ca2PN3:Eu2+ as a promising broad‐band red‐emitter (λem=650 nm; fwhm=1972 cm−1). Besides simple handling, the presented synthetic method offers access to large sample volumes, and the underlying reaction conditions facilitate single‐crystal growth, required for excellent optical properties.