Nitride Spinel: An Ultraincompressible High-Pressure Form of BeP2N4

Owing to its outstanding elastic properties, the nitride spinel γ-Si₃N₄ is of considered interest for materials scientists and chemists. DFT calculations suggest that Si₃N₄-analog beryllium phosphorus nitride BeP₂N₄ adopts the spinel structure at elevated pressures as well and shows outstanding elastic properties. Herein, we investigate phenakite-type BeP₂N₄ by single-crystal synchrotron X-ray diffraction and report the phase transition into the spinel-type phase at 47 GPa and 1800 K in a laser-heated diamond anvil cell. The structure of spinel-type BeP₂N₄ was refined from pressure-dependent in situ synchrotron powder X-ray diffraction measurements down to ambient pressure, which proves spinel-type BeP₂N₄ a quenchable and metastable phase at ambient conditions. Its isothermal bulk modulus was determined to 325(8) GPa from equation of state, which indicates that spinel-type BeP₂N₄ is an ultraincompressible material.     

United in Nitride: The Highly Condensed Boron Phosphorus Nitride BP3N6

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.     

Accessing Tetravalent Transition‐Metal Nitridophosphates through High‐Pressure Metathesis

Advancing the attainable composition space of a compound class can lead to fascinating materials. The first tetravalent metal nitridophosphate, namely Hf_9?xP₂₄N_52?4xO_4x (x≈1.84), was prepared by high‐pressure metathesis. The Group 4 nitridophosphates are now an accessible class of compounds. The high‐pressure metathesis reaction using a multianvil setup yielded single crystals that were suitable for structure analysis. Magnetic properties of the compound indicate Hf in oxidation state +IV. Optical measurements show a band gap in the UV region. The presented route unlocks the new class of Group 4 nitridophosphates by significantly improving the understanding of this nitride chemistry. Hf_9?xP₂₄N_52?4xO_4x (x≈1.84) is a model system and its preparation is the first step towards a systematic exploration of the transition‐metal nitridophosphates.     

A High‐Pressure Polymorph of Phosphorus Nitride Imide

Phosphorus nitride imide, PN(NH), is of great scientific importance because it is isosteric with silica (SiO₂). Accordingly, a varied structural diversity could be expected. However, only one polymorph of PN(NH) has been reported thus far. Herein, we report on the synthesis and structural investigation of the first high‐pressure polymorph of phosphorus nitride imide, β‐PN(NH); the compound has been synthesized using the multianvil technique. By adding catalytic amounts of NH₄Cl as a mineralizer, it became possible to grow single crystals of β‐PN(NH), which allowed the first complete structural elucidation of a highly condensed phosphorus nitride from single‐crystal X‐ray diffraction data. The structure was confirmed by FTIR and ³¹P and ¹H solid‐state NMR spectroscopy. We are confident that high‐pressure/high‐temperature reactions could lead to new polymorphs of PN(NH) containing five‐fold‐ or even six‐fold‐coordinated phosphorus atoms and thus rivalling or even surpassing the structural variety of SiO₂.     

Open‐Shell 3d Transition Metal Nitridophosphates MIIP8N14 (MII=Fe,Co, Ni) by High‐Pressure Metathesis

3d transition metal nitridophosphates M^IIP₈N₁₄ (M^II=Fe, Co, Ni) were prepared by high‐pressure metathesis indicating that this route might give a systematic access to a structurally rich family of M‐P‐N compounds. Their structures, which are stable in air up to at least 1273 K, were determined through powder X‐ray diffraction and consist of highly condensed tetra‐layers of PN₄ tetrahedra and MN₆ octahedra. Magnetic measurements revealed paramagnetic behavior of CoP₈N₁₄ and NiP₈N₁₄ down to low temperatures while, FeP₈N₁₄ exhibits an antiferromagnetic transition at T_N=3.5(1) K. Curie–Weiss fits of the paramagnetic regime indicate that the transition metal cations are in a oxidation state +II, which was corroborated by Mössbauer spectroscopy for FeP₈N₁₄. The ligand field exerted by the nitride ions in CoP₈N₁₄ and NiP₈N₁₄ was determined from UV/Vis/NIR data and is comparable to that of aqua‐ligands and oxophosphates.     

Pressure‐Tuneable Visible‐Range Band Gap in the Ionic Spinel Tin Nitride

The application of pressure allows systematic tuning of the charge density of a material cleanly, that is, without changes to the chemical composition via dopants, and exploratory high‐pressure experiments can inform the design of bulk syntheses of materials that benefit from their properties under compression. The electronic and structural response of semiconducting tin nitride Sn₃N₄ under compression is now reported. A continuous opening of the optical band gap was observed from 1.3 eV to 3.0 eV over a range of 100 GPa, a 540 nm blue‐shift spanning the entire visible spectrum. The pressure‐mediated band gap opening is general to this material across numerous high‐density polymorphs, implicating the predominant ionic bonding in the material as the cause. The rate of decompression to ambient conditions permits access to recoverable metastable states with varying band gaps energies, opening the possibility of pressure‐tuneable electronic properties for future applications.     

Pentacoordinate Phosphorus in a High‐Pressure Polymorph of Phosphorus Nitride Imide P4N6(NH)

Coordination numbers higher than usual are often associated with superior mechanical properties. In this contribution we report on the synthesis of the high‐pressure polymorph of highly condensed phosphorus nitride imide P₄N₆(NH) representing a new framework topology. This is the first example of phosphorus in trigonal‐bipyramidal coordination being observed in an inorganic network structure. We were able to obtain single crystals and bulk samples of the compound employing the multi‐anvil technique. γ‐P₄N₆(NH) has been thoroughly characterized using X‐ray diffraction, solid‐state NMR and FTIR spectroscopy. The synthesis of γ‐P₄N₆(NH) gives new insights into the coordination chemistry of phosphorus at high pressures. The synthesis of further high‐pressure phases with higher coordination numbers exhibiting intriguing physical properties seems within reach.     

Double Double Cation Order in the High‐Pressure Perovskites MnRMnSbO6

Cation ordering in ABO₃ perovskites adds to their chemical variety and can lead to properties such as ferrimagnetism and magnetoresistance in Sr₂FeMoO₆. Through high‐pressure and high‐temperature synthesis, a new type of “double double perovskite” structure has been discovered in the family MnRMnSbO₆ (R=La, Pr, Nd, Sm). This tetragonal structure has a 1:1 order of cations on both A and B sites, with A‐site Mn²⁺ and R³⁺ cations ordered in columns and Mn²⁺ and Sb⁵⁺ having rock salt order on the B sites. The MnRMnSbO₆ double double perovskites are ferrimagnetic at low temperatures with additional spin‐reorientation transitions. The ordering direction of ferrimagnetic Mn spins in MnNdMnSbO₆ changes from parallel to [001] below T_C=76 K to perpendicular below the reorientation transition at 42 K at which Nd moments also order. Smaller rare earths lead to conventional monoclinic double perovskites (MnR)MnSbO₆ for Eu and Gd.     

High‐Pressure Synthesis of a Nitrogen‐Rich Inclusion Compound ReN8⋅x N2 with Conjugated Polymeric Nitrogen Chains

A nitrogen‐rich compound, ReN₈?x N₂, was synthesized by a direct reaction between rhenium and nitrogen at high pressure and high temperature in a laser‐heated diamond anvil cell. Single‐crystal X‐ray diffraction revealed that the crystal structure, which is based on the ReN₈ framework, has rectangular‐shaped channels that accommodate nitrogen molecules. Thus, despite a very high synthesis pressure, exceeding 100 GPa, ReN₈?x N₂ is an inclusion compound. The amount of trapped nitrogen (x) depends on the synthesis conditions. The polydiazenediyl chains [?N=N?]_∞ that constitute the framework have not been previously observed in any compound. Ab initio calculations on ReN₈?x N₂ provide strong support for the experimental results and conclusions.     

Stishovite's Relative: A Post‐Coesite Form of Phosphorus Oxonitride

Phosphorus oxonitride (PON) is isoelectronic with SiO₂ and may exhibit a similar broad spectrum of intriguing properties as silica. However, PON has only been sparsely investigated under high‐pressure conditions and there has been no evidence on a PON polymorph with a coordination number of P greater than 4. Herein, we report a post‐coesite (pc) PON polymorph exhibiting a stishovite‐related structure with P in a (5+1) coordination. The pc‐PON was synthesized using the multianvil technique and characterized by powder X‐ray diffraction, solid‐state NMR spectroscopy, TEM measurements and in situ synchrotron X‐ray diffraction in diamond anvil cells. The structure model was verified by single‐crystal X‐ray diffraction at 1.8 GPa and the isothermal bulk modulus of pc‐PON was determined to K₀=163(2) GPa. Moreover, an orthorhombic PON polymorph (o‐PON) was observed under high‐pressure conditions and corroborated as the stable modification at pressures above 17 GPa by DFT calculations.     

Phenakite‐Type BeP2N4—A Possible Precursor for a New Hard Spinel‐Type Material

BeP₂N₄ was synthesized in a multi‐anvil apparatus starting from Be₃N₂ and P₃N₅ at 5 GPa and 1500 °C. The compound crystallizes in the phenakite structure type (space group R$\bar 3$ , no. 148) with a=1269.45(2) pm, c=834.86(2) pm, V=1165.13(4)×10⁶ pm³ and Z=18. As isostructural and isovalence‐electronic α‐Si₃N₄ transforms into β‐Si₃N₄ at high pressure and temperature, we studied the phase transition of BeP₂N₄ into the spinel structure type by using density functional theory calculations. The predicted transition pressure of 24 GPa is within the reach of today’s state of the art high‐pressure experimental setups. Calculations of inverse spinel‐type BeP₂N₄ revealed this polymorph to be always higher in enthalpy than either phenakite‐type or spinel‐type BeP₂N₄. The predicted bulk modulus of spinel‐type BeP₂N₄ is in the range of corundum and γ‐Si₃N₄ and about 40 GPa higher than that of phenakite‐type BeP₂N₄. This finding implies an increase in hardness in analogy to that occurring for the β‐ to γ‐Si₃N₄ transition. In hypothetical spinel‐type BeP₂N₄ the coordination number of phosphorus is increased from 4 to 6. So far only coordination numbers up to 5 have been experimentally realized (γ‐P₃N₅), though a sixfold coordination for P has been predicted for hypothetic δ‐P₃N₅. We believe, our findings provide a strong incentive for further high‐pressure experiments in the quest for novel hard materials with yet unprecedented structural motives.     

High-Pressure Synthesis of Sc5P12N23O3 and Ti5P12N24O2 by Activation of the Binary Nitrides ScN and TiN with NH4F

Multinary transition metal nitrides and oxonitrides are a versatile and intriguing class of compounds. However, they have been investigated far less than pure oxides. The compounds Sc₅P₁₂N₂₃O₃ and Ti₅P₁₂N₂₄O₂ have now been synthesized from the binary nitrides ScN and TiN, respectively, by following a high-pressure high-temperature approach at 8 GPa and 1400 °C. NH₄F acts as a mineralizing agent that supports product formation and crystallization. The starting materials ScN and TiN are seemingly an uncommon choice because of their chemical inertness but, nevertheless, react under these conditions. Sc₅P₁₂N₂₃O₃ and Ti₅P₁₂N₂₄O₂ crystallize isotypically with Ti₅B₁₂O₂₆, consisting of solely vertex-sharing P(O/N)₄ tetrahedra forming two independent interpenetrating diamond-like nets that host TM(O/N)₆ (TM=Sc, Ti) octahedra. Ti₅P₁₂N₂₄O₂ is a mixed-valence compound and shows ordering of Ti³⁺ and Ti⁴⁺ ions.     

A High‐Pressure Polymorph of Phosphorus Oxonitride with the Coesite Structure

The chemical and physical properties of phosphorus oxonitride (PON) closely resemble those of silica, to which it is isosteric. A new high‐pressure phase of PON is reported herein. This polymorph, synthesized by using the multianvil technique, crystallizes in the coesite structure. This represents the first occurrence of this very dense network structure outside of SiO₂. Phase‐pure coesite PON (coe‐PON) can be synthesized in bulk at pressures above 15 GPa. This compound was thoroughly characterized by means of powder X‐ray diffraction, DFT calculations, and FTIR and MAS NMR spectroscopy, as well as temperature‐dependent diffraction. These results represent a major step towards the exploration of the phase diagram of PON at very high pressures and the possibly synthesis of a stishovite‐type PON containing hexacoordinate phosphorus.     

Manipulating Layered P2@P3 Integrated Spinel Structure Evolution for High‐Performance Sodium‐Ion Batteries

Structural evolution of the cathode during cycling plays a vital role in the electrochemical performance of sodium‐ion batteries. A strategy based on engineering the crystal structure coupled with chemical substitution led to the design of the layered P2@P3 integrated spinel oxide cathode Na_0.5Ni_0.1Co_0.15Mn_0.65Mg_0.1O₂, which shows excellent sodium‐ion half/full battery performance. Combined analyses involving scanning transmission electron microscopy with atomic resolution as well as in situ synchrotron‐based X‐ray absorption spectra and in situ synchrotron‐based X‐ray diffraction patterns led to visualization of the inherent layered P2@P3 integrated spinel structure, charge compensation mechanism, structural evolution, and phase transition. This study provides an in‐depth understanding of the structure‐performance relationship in this structure and opens up a novel field based on manipulating structural evolution for the design of high‐performance battery cathodes.     

Nitridophosphate-Based Ultra-Narrow-Band Blue-Emitters: Luminescence Properties of AEP8N14:Eu2+ (AE=Ca,Sr, Ba)

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 (λ_em=470 nm; fwhm=1380 cm⁻¹) and SrP₈N₁₄ (λ_em=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 (λ_em=417/457 nm; fwhm=2075/3550 cm⁻¹).     

High‐Pressure Phase Transformations in TiPO4: A Route to Pentacoordinated Phosphorus

Titanium(III) phosphate, TiPO₄ , is a typical example of an oxyphosphorus compound containing covalent P?O bonds. Single‐crystal X‐ray diffraction studies of TiPO₄ reveal complex and unexpected structural and chemical behavior as a function of pressure at room temperature. A series of phase transitions lead to the high‐pressure phase V, which is stable above 46 GPa and features an unusual oxygen coordination of the phosphorus atoms. TiPO₄‐V is the first inorganic phosphorus‐containing compound that exhibits fivefold coordination with oxygen. Up to the highest studied pressure of 56 GPa, TiPO₄‐V coexists with TiPO₄‐IV, which is less dense and might be kinetically stabilized. Above a pressure of about 6 GPa, TiPO₄‐II is found to be an incommensurately modulated phase whereas a lock‐in transition at about 7 GPa leads to TiPO₄‐III with a fourfold superstructure compared to the structure of TiPO₄‐I at ambient conditions. TiPO₄‐II and TiPO₄‐III are similar to the corresponding low‐temperature incommensurate and commensurate magnetic phases and reflect the strong pressure dependence of the spin‐Peierls interactions.