Owing to intriguing materials properties non-metal nitrides are of special interest for both, solid-state chemistry and materials science. Mixed ternary non-metal nitrides, however, have only been sparsely investigated, as preparative chemistry lacks a systematic access, yet. Herein, we report on the highly condensed boron phosphorus nitride BP N , which was synthesized from (PNCl ) , NH N and h-BN in a high-pressure high-temperature reaction. By increasing partial pressure of HCl during synthesis using NH Cl, single-crystals of BP N up to 80 μm in length were obtained. The unprecedented framework-type structure determined by single-crystal XRD blends structural motifs of both, α-P N and c-BN, rendering BP N a double nitride. The compound was further investigated by Rietveld refinement, EDX, temperature-dependent PXRD, FTIR and solid-state NMR spectroscopy. The formation of BP N through use of reactive precursors exemplifies an innovative access to mixed non-metal nitrides.

Non‐metal nitrides such as BN, Si3N4, and P3N5 meet numerous demands on high‐performance materials, and their high‐pressure polymorphs exhibit outstanding mechanical properties. Herein, we present the silicon phosphorus nitride imide SiP2N4NH featuring sixfold coordinated Si. Using the multi‐anvil technique, SiP2N4NH was obtained by high‐pressure high‐temperature synthesis at 8 GPa and 1100 °C with in situ formed HCl acting as a mineralizer. Its structure was elucidated by a combination of single‐crystal X‐ray diffraction and solid‐state NMR measurements. Moreover, SiP2N4NH was characterized by energy‐dispersive X‐ray spectroscopy and (temperature‐dependent) powder X‐ray diffraction. The highly condensed Si/P/N framework features PN4 tetrahedra as well as the rare motif of SiN6 octahedra, and is discussed in the context of ambient‐pressure motifs competing with close‐packing of nitride anions, representing a missing link in the high‐pressure chemistry of non‐metal nitrides.

Owing to intriguing materials properties non‐metal nitrides are of special interest for both, solid‐state chemistry and materials science. Mixed ternary non‐metal nitrides, however, have only been sparsely investigated, as preparative chemistry lacks a systematic access, yet. Herein, we report on the highly condensed boron phosphorus nitride BP3N6, which was synthesized from (PNCl2)3, NH4N3 and h‐BN in a high‐pressure high‐temperature reaction. By increasing partial pressure of HCl during synthesis using NH4Cl, single‐crystals of BP3N6 up to 80 μm in length were obtained. The unprecedented framework‐type structure determined by single‐crystal XRD blends structural motifs of both, α‐P3N5 and c‐BN, rendering BP3N6 a double nitride. The compound was further investigated by Rietveld refinement, EDX, temperature‐dependent PXRD, FTIR and solid‐state NMR spectroscopy. The formation of BP3N6 through use of reactive precursors exemplifies an innovative access to mixed non‐metal nitrides.

Non-metal nitrides such as BN,Si 3 N 4 ,and P 3 N 5 meet numerous demands on high-performance materials,a nd their high-pressure polymorphs exhibit outstanding mechanical properties.H erein, we present the silicon phosphorus nitride imide SiP 2 N 4 NH featuring sixfold coordinated Si. Using the multi-anvil technique, SiP 2 N 4 NH was obtained by highpressure high-temperature synthesis at 8GPa and 1100 8 8C with in situ formed HCl acting as am ineralizer. Its structure was elucidated by ac ombination of single-crystal X-ray diffraction and solid-state NMR measurements.M oreover, SiP 2 N 4 NH was characterized by energy-dispersive X-ray spectroscopya nd (temperature-dependent) powder X-ray diffraction. The highly condensed Si/P/N framework features PN 4 tetrahedra as well as the rare motif of SiN 6 octahedra, and is discussed in the context of ambient-pressure motifs competing with close-packing of nitride anions,representing amissing link in the high-pressure chemistry of non-metal nitrides.