United in Nitride: The Highly Condensed Boron Phosphorus Nitride BP₃N₆

Abstract

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.

Nitridophosphate – eine Erfolgsgeschichte der Nitridsynthese

“…[25][26][27][28] Ein Doppelnitrid ist allerdings nicht direkt mit einem Doppeloxid vergleichbar, da sich Letzteres auf Kationen mit ähnlicher Elektronegativitätbezieht. [25][26][27][28] Ein Doppelnitrid ist allerdings nicht direkt mit einem Doppeloxid vergleichbar, da sich Letzteres auf Kationen mit ähnlicher Elektronegativitätbezieht.…”

“…B. anhand von b-HPN 2 ,M H 4 P 6 N 12 (M = Mg, Ca, Sr), SrP 3 N 5 NH und den MP 2 N 4 -Phasen (M = Ca, Sr, Ba) gezeigt wurde (siehe Abschnitte 2u nd 3). [27] Das HCl schaffte es sogar, h-BN zu aktivieren, woraus sich regelmäßig geformte Einkristalle gebildet haben (Abbildung 12). Diese Hypothese wird auch anhand des Beispiels des Borphosphornitrids BP 3 N 6 gestützt [Gl.…”

“…b) Kristallstruktur von BP 3 N 6 mit hervorgehobenen BN 4 -(grün) und PN 4 -Tetraedern (blau und rot). [27] . [27] .…”

Rivalry under Pressure: The Coexistence of Ambient‐Pressure Motifs and Close‐Packing in Silicon Phosphorus Nitride Imide SiP2N4NH

“…[5,17,18] Entire sixfold Ncoordination of P and Si has been proposed by DFT calculations at 35.5 GPa in V 3 O 5 -type P 3 N 5 and 160 GPa in CaTi 2 O 4 -related Si 3 N 4 ,which can both be derived from ac lose-packing of nitride anions. [24] Its structure blends motifs of a-P 3 N 5 and c-BN,b ut cannot be derived from any close-packing. [24] Its structure blends motifs of a-P 3 N 5 and c-BN,b ut cannot be derived from any close-packing.…”

“…Theh ighest yield, however, was achieved with an excess of (PNCl 2 ) 3 ( 2) and NH 4 N 3 ( 2.5). [24,27,28] [24,27,28] …”