Single‐Bonded Cubic AsN from High‐Pressure and High‐Temperature Chemical Reactivity of Arsenic and Nitrogen

Abstract

Chemical reactivity between As and N 2 ,l eading to the synthesis of crystalline arsenic nitride,i sh ere reported under high pressure and high temperature conditions generated by laser heating in ad iamond anvil cell. Single-crystal synchrotron X-rayd iffraction at different pressures between 30 and 40 GPaprovides evidence for the synthesis of acovalent compound of AsN stoichiometry,crystallizing in acubic P2 1 3 space group,inwhich eachofthe two elements is single-bonded to three atoms of the other and hosts an electron lone pair,i n at etrahedral anisotropic coordination. The identification of characteristic structural motifs highlights the key role played by the directional repulsive interactions between non-bonding electron lone pairs in the formation of the AsN structure. Additional data indicate the existence of AsN at room temperature from 9.8 up to 50 GPa. Implications concern fundamental aspects of pnictogens chemistry and the synthesis of innovative advanced materials.

Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′‐P3N5, δ‐P3N5 and PN2

“…While transformation from XN 4 to XN 6 units was already observed in binary group 14 element nitrides (SiN 2 , GeN 2 , SnN 2 ) [15] and a chalcogen nitride (SN 2 ) produced under pressure, [16] XN 6 octahedra are still eluding binary pnictogen nitrides [17–19] . This gap in our empirical understanding of non‐metal nitrides is especially striking given the significant efforts that were devoted to their synthesis, particularly for binary phosphorus nitrides.…”

“…While transformation from XN 4 to XN 6 units was already observed in binary group 14 element nitrides (SiN 2 , GeN 2 , SnN 2 ) [15] and a chalcogen nitride (SN 2 ) produced under pressure, [16] XN 6 octahedra are still eluding binary pnictogen nitrides. [ 17 , 18 , 19 ] This gap in our empirical understanding of non‐metal nitrides is especially striking given the significant efforts that were devoted to their synthesis, particularly for binary phosphorus nitrides. Still, the many experimental studies,[ 18 , 19 , 20 , 21 ] supported by theoretical calculations,[ 14 , 22 , 23 ] amounted to the synthesis of three P 3 N 5 polymorphs, namely α‐ and β‐P 3 N 5 , both formed at near ambient conditions,[ 18 , 20 ] and γ‐P 3 N 5 produced at 11 GPa and 1500 K. [19] The exact crystal structure of β‐P 3 N 5 is still unknown.…”

High-Pressure and High-Temperature Chemistry of Phosphorus and Nitrogen: Synthesis and Characterization of α- and γ-P3N5

“…Within this picture, P was used as a reactant and laser absorber, whereas N 2 was used as a reactant and PTM, thus avoiding any unnecessary contamination source. The same approach was successfully adopted to induce chemical reactivity in P and H 2 , leading to the synthesis of PH 3 and to the discovery of the crystalline van der Waals compound (PH 3 ) 2 H 2 25 and, more recently, to the synthesis of crystalline arsenic nitride (AsN) from As and N 2 . 26 While this manuscript was in preparation, a paper on the same topic was published by a Japanese group led by Hasegawa.…”

High‐pressure and high‐temperature synthesis of crystalline Sb3N5

“…Based on existing literature data, the HP-HT conditions, at which chemical reactivity was detected, correspond to the fluid phase of Sb [35] and N 2 . [36] Noticeably, also in the case of P [7] and likely in that of As, [9] reactivity with N 2 appears to take place in the fluid phase in this pressure regime.…”