A New Family of High Oxidation State Antiperovskite Nitrides: La3MN5 (M = Cr, Mn and Mo).

Three new nitrides La3MN5 (M = Cr, Mn, and Mo) have been synthesized using a high pressure azide route. These are the first examples of ternary Cs3CoCl5-type nitrides, and show that this (MN4)NLa3 antiperovskite structure type may be used to stabilise high oxidation-state transition metals in tetrahedral molecular [MN4]n- nitridometallate anions. Magnetic measurements confirm that Cr and Mo are in the M6+ state, but the M = Mn phase has an anomalously small paramagnetic moment and large cell volume. Neutron powder diffraction data are fitted using an anion-excess La3MnN5.30 model (space group I4/mcm, a = 6.81587(9) Å and c = 11.22664(18) Å at 200 K) in which Mn is close to the +7 state. Excess-anion incorporation into Cs3CoCl5-type materials has not been previously reported, and this or other substitution mechanisms may enable many other high oxidation state transition metal nitrides to be prepared.

Please Mind the Gap: Highly Condensed P-N Networks in LiP4 N7 and Li3-x P6 N11-x (NH)x.

Alkali nitridophosphates AP4 N7 and A3 P6 N11 (A=Na, K, Rb, Cs) have been known for decades. However, their Li homologues have remained elusive. In this work, the highly condensed lithium (imido)nitridophosphates LiP4 N7 and Li3-x P6 N11-x (NH)x (x=1.66(3)) were synthesized from LiPN2 and P3 N5 in the multianvil press at 10 GPa. They constitute the first lithium nitridophosphates with 3D networks exhibiting a degree of condensation larger than 0.5 and high thermal stability. LiP4 N7 crystallizes in the orthorhombic space group P21 21 21 with a=4.5846(6) Å, b=8.0094(11) Å, and c=13.252(2) Š(Z=4). Li3-x P6 N11-x (NH)x crystallizes in the triclinic space group P 1 - ${\mathrel{\mathop{{\rm { 1}}}\limits^{{\rm -}}}}$ with Z=2, a=4.6911(11) Å, b=7.024(2) Å, c=12.736(3) Å, α=87.726(11), ß=80.279(11), and γ=70.551(12)°. Both compounds are stable against hydrolysis in air.

Defect rocksalt structures in the La-Na-N system.

Sodium azide (NaN3) is a versatile nitrogen source that can be used for the synthesis of new nitrides under high-pressure and temperature conditions. Reactions between lanthanum nitride (LaN) and sodium azide (NaN3) at 800°C under 8 GPa pressure have led to the discovery of two defect rocksalt phases which are the first reported ternaries in the La-Na-N system. Preliminary structure assignments have been made based on fits to powder X-ray diffraction profiles. One phase is La1-xNa3xN with vacancies at octahedral La sites and interstitial tetrahedral Na cations. This phase has a tetragonally distorted rocksalt structure (space group I4[Formula: see text]mmm, a = 3.8704(2) and c = 5.2098(3) Å for nominal x = 0.10) and the distortion decreases with increasing Na content (space group I4[Formula: see text]mmm, a = 3.8060(2) Å, c = 5.2470(3) Å for nominal x = 0.14), further giving a cubic phase (a = 5.3055(2) Å) for nominal x = 0.25. This coexists with another cubic [Formula: see text] phase (a = 5.1561 (5) Å), tentatively identified as rocksalt 'NaN1/3' stabilized by a small amount of La; NaLayN(1+3y)/3 with y ≈ 1%. These initial investigations reveal that the high-pressure La-Na-N phase diagram may be rich in defect rocksalt-type materials although further work using neutron diffraction will be needed to confirm the structures. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Low-dimensional magnetism in calcium nitridonickelate(II) Ca2NiN2.

Calcium nitridonickelate(II) Ca2NiN2 has been prepared through a high-temperature and high-pressure azide-mediated redox reaction, demonstrating that this method can stabilise nitrides of late transition metals in relatively high oxidation states. Ca2NiN2 crystallizes in the Na2HgO2 structure type and displays low-dimensional antiferromagnetic ordering of Ni2+ spins.

Preparation of Bulk-Phase Nitride Perovskite LaReN3 and Topotactic Reduction to LaNiO2 -Type LaReN2.

While halide and oxide perovskites are numerous and many display outstanding properties, ABN3 perovskite nitrides are extremely rare due to synthetic challenges arising from the low chemical potential of nitrogen and a tendency to form low-coordination nitridometallate anions. We report the preparation of a perovskite nitride LaReN3 through azide-mediated oxidation at high pressure. High-resolution synchrotron diffraction shows that LaReN3 has a low-symmetry, triclinic, perovskite superstructure resulting from orbital ordering with strong spin-orbit coupling distortions. Topotactic reduction of LaReN3 above 500 °C leads to layered tetragonal LaReN2 via a probable LaReN2.5 intermediate, which is the first reported example of nitride defect perovskites. Magnetisation and conductivity measurements indicate that LaReN3 and LaReN2 are both metallic solids. The two chemical approaches presented are expected to lead to new classes of ABN3 and defect ABN3-x nitride perovskite materials.

Preparation of iron(IV) nitridoferrate Ca4FeN4 through azide-mediated oxidation under high-pressure conditions.

Transition metal nitrides are an important class of materials with applications as abrasives, semiconductors, superconductors, Li-ion conductors, and thermoelectrics. However, high oxidation states are difficult to attain as the oxidative potential of dinitrogen is limited by its high thermodynamic stability and chemical inertness. Here we present a versatile synthesis route using azide-mediated oxidation under pressure that is used to prepare the highly oxidised ternary nitride Ca4FeN4 containing Fe4+ ions. This nitridometallate features trigonal-planar [FeN3]5- anions with low-spin Fe4+ and antiferromagnetic ordering below a Neel temperature of 25 K, which are characterised by neutron diffraction, 57Fe-Mössbauer and magnetisation measurements. Azide-mediated high-pressure synthesis opens a way to the discovery of highly oxidised nitrides.

Nitride Spinel: An Ultraincompressible High-Pressure Form of BeP2 N4.

Owing to its outstanding elastic properties, the nitride spinel γ-Si3 N4 is of considered interest for materials scientists and chemists. DFT calculations suggest that Si3 N4 -analog beryllium phosphorus nitride BeP2 N4 adopts the spinel structure at elevated pressures as well and shows outstanding elastic properties. Herein, we investigate phenakite-type BeP2 N4 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 BeP2 N4 was refined from pressure-dependent in situ synchrotron powder X-ray diffraction measurements down to ambient pressure, which proves spinel-type BeP2 N4 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 BeP2 N4 is an ultraincompressible material.

The Long-Periodic Loop-Branched Chain Structure of the Oxonitridophosphate La21 P40 O46 N57 , Elucidated by a Combination of TEM and Microfocused Synchrotron Radiation.

The lanthanum oxonitridophosphate La21 P40 O46 N57 was synthesized by high-pressure metathesis from partially hydrolysed LiPN2 and LaCl3 at 750-950 °C and 7-9 GPa. The combination of transmission electron microscopy (TEM) and diffraction using microfocused synchrotron radiation revealed a monoclinic crystal structure (space group P21 /n, a=14.042(4), b=7.084(3), c=41.404(10) Å, ß=97.73(3)° and Z=2), which is characterized by loop-branched 21 member single chains of P(O,N)4 tetrahedra that extend along [2 0 1]. These chains are related to the loop-branched dreier single chains with dreier-ring loops in stillwellite (CeBSiO5 ). In La21 P40 O46 N57 , these chains are characterized by a complex long-periodic conformation and exhibit disorder that involves La/N and P split positions. This is an extraordinarily long periodicity with respect to branched single chains of tetrahedra. La21 P40 O46 N57 constitutes the first rare-earth oxonitridophosphate exhibiting a chain structure. Single-crystal data are consistent with electron and powder X-ray diffraction.

Boron Phosphorus Nitride at Extremes: PN6 Octahedra in the High-Pressure Polymorph ß-BP3 N6.

The high-pressure behavior of non-metal nitrides is of special interest for inorganic and theoretical chemistry as well as materials science, as these compounds feature intriguing elastic properties. The double nitride α-BP3 N6 was investigated by in situ single-crystal X-ray diffraction (XRD) upon cold compression to a maximum pressure of about 42 GPa, and its isothermal bulk modulus at ambient conditions was determined to be 146(6) GPa. At maximum pressure the sample was laser-heated, which resulted in the formation of an unprecedented high-pressure polymorph, ß-BP3 N6 . Its structure was elucidated by single-crystal XRD, and can be described as a decoration of a distorted hexagonal close packing of N with B in tetrahedral and P in octahedral voids. Hence, ß-BP3 N6 is the first nitride to contain PN6 octahedra, representing the much sought-after proof of principle for sixfold N-coordinated P that has been predicted for numerous high-pressure phases of nitrides.

Open-Shell 3d Transition Metal Nitridophosphates MII P8 N14 (MII =Fe, Co, Ni) by High-Pressure Metathesis.

3d transition metal nitridophosphates MII P8 N14 (MII =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 CoP8 N14 and NiP8 N14 down to low temperatures while, FeP8 N14 exhibits an antiferromagnetic transition at TN =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 FeP8 N14 . The ligand field exerted by the nitride ions in CoP8 N14 and NiP8 N14 was determined from UV/Vis/NIR data and is comparable to that of aqua-ligands and oxophosphates.

Nitridophosphates: A Success Story of Nitride Synthesis.

Nitridophosphates and phosphorus nitrides are thoroughly investigated classes of nitrides. During thirty years of research, the methods for their synthesis evolved from the condensation of molecular precursors at moderate temperatures and ambient pressures to state-of-the-art high-pressure and high-temperature processes. Landmark breakthroughs made in recent years led to a comprehension-based proficiency in nitridophosphate synthesis that is illustrated by the large compositional and structural diversity of the nitridophosphates known today. Herein, we review the advances made in synthesis with regard to the prevalent problem of nitride synthesis: the susceptibility of nitride ions to oxidation.

LiPr2P4N7O3: Structural Diversity of Oxonitridophosphates Accessed by High-Pressure Metathesis.

The structural diversity of tetrahedra networks of phosphates can greatly be enhanced by introduction of mixed N/O anion positions. LiPr2P4N7O3 exemplifies the benefits of N/O mixed anion positions as it is the first rare-earth (oxo)nitridophosphate with a single-layered structure and a degree of condensation (atomic ratio of tetrahedra centers (P) to tetrahedra corners (N/O atoms)) of 2/5. The compound was prepared through high-pressure metathesis starting from PrF3, LiPN2, Li2O, and PON using a hydraulic 1000t press and the multianvil technique. LiPr2P4N7O3 crystallizes as pale-green single-crystals, from which its structure was determined (space group P21/ c (no. 14), a = 4.927(1), b = 7.848(2), c = 10.122(2) Å, ß = 91.55(3)°, Z = 2, R1 = 0.020, wR2 = 0.045). The structure consists of single-layers of vertex-sharing Q3-type P(N/O)4 tetrahedra forming four- and eight-membered rings arranged in the fashion of the Archimedean fes net. UV-vis spectroscopy revealed the typical Pr3+ f -f transitions, leading to a pale-green color of the crystals. Moreover, the optical band gap was determined to 4.1(1) eV, assuming a direct transition. High-temperature powder X-ray diffraction showed the beginning of a gradual decomposition starting at ca. 500 °C.

High-Pressure Metathesis of the M1- xPO3+4 xN1-4 x ( x ≈ 0.05) and M0.75PO4 ( M = Zr, Hf) Orthophosphates.

We describe the oxonitridophosphates M1- xPO3+4 xN1-4 x ( x ≈ 0.05) and the isotypic oxophosphates M0.75PO4 ( M = Zr, Hf) obtained by high-pressure metathesis. The structures (ZrSiO4-type, space group I41/ amd (no. 141), a = 6.5335(7)-6.6178(12), c = 5.7699(7)-5.8409(9) Å, Z = 4) were refined from single-crystal X-ray diffraction data, and the powder samples were examined with quantitative Rietveld refinement. Infrared spectroscopy did not indicate the presence of X-H ( X = O, N) bonds. The optical band gaps, between 3.5 and 4.3 eV, were estimated from UV-vis data using the Kubelka-Munk function under assumption of a direct band gap. Temperature-dependent powder X-ray diffraction showed a phase transformation of the M0.75PO4 ( M = Zr, Hf) compounds to ambient pressure polymorphs at 780 (Zr) and 900 °C (Hf). The preparation of the nitrogen containing compounds exemplifies the systematic access to the new class of group 4 nitridophosphates granted by high-pressure metathesis. Moreover, we show that high-pressure metathesis can also be used for the preparation of metastable oxophosphates.

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 Hf9-x P24 N52-4x O4x (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. Hf9-x P24 N52-4x O4x (x≈1.84) is a model system and its preparation is the first step towards a systematic exploration of the transition-metal nitridophosphates.

Puzzling Intergrowth in Cerium Nitridophosphate Unraveled by Joint Venture of Aberration-Corrected Scanning Transmission Electron Microscopy and Synchrotron Diffraction.

Thorough investigation of nitridophosphates has rapidly accelerated through development of new synthesis strategies. Here we used the recently developed high-pressure metathesis to prepare the first rare-earth metal nitridophosphate, Ce4Li3P18N35, with a high degree of condensation >1/2. Ce4Li3P18N35 consists of an unprecedented hexagonal framework of PN4 tetrahedra and exhibits blue luminescence peaking at 455 nm. Transmission electron microscopy (TEM) revealed two intergrown domains with slight structural and compositional variations. One domain type shows extremely weak superstructure phenomena revealed by atomic-resolution scanning TEM (STEM) and single-crystal diffraction using synchrotron radiation. The corresponding superstructure involves a modulated displacement of Ce atoms in channels of tetrahedra 6-rings. The displacement model was refined in a supercell as well as in an equivalent commensurate (3 + 2)-dimensional description in superspace group P63(α, ß, 0)0(-α - ß, α, 0)0. In the second domain type, STEM revealed disordered vacancies of the same Ce atoms that were modulated in the first domain type, leading to sum formula Ce4-0.5xLi3P18N35-1.5xO1.5x (x ≈ 0.72) of the average structure. The examination of these structural intricacies may indicate the detection limit of synchrotron diffraction and TEM. We discuss the occurrence of either Ce displacements or Ce vacancies that induce the incorporation of O as necessary stabilization of the crystal structure.

High-Pressure Synthesis of Melilite-type Rare-Earth Nitridophosphates RE2P3N7 and a Ba2Cu[Si2O7]-type Polymorph.

High-pressure metathesis was proposed to be a gateway to the elusive class of rare-earth nitridophosphates. With this method the first ternary compounds of this class with sum formula RE2P3N7 were prepared, a melilite-type with RE = Pr, Nd, Sm, Eu, Ho, Yb (Ho2P3N7: P4̅21m, a = 7.3589(2), c = 4.9986(2) Å, Z = 2) and a Ba2Cu[Si2O7] structure type with RE = La, Ce, Pr (Pr2P3N7: monoclinic, C2/c, a = 7.8006(3), b = 10.2221(3), c = 7.7798(3) Å, ß = 111.299(1)°, Z = 4). The phase relation between the two structure types was prior unknown and is here evidenced by experimental data as well as density functional theory calculations performed for the Pr2P3N7 compounds. Adequate classification of both structures types with regard to Liebau nomenclature, vertex symbol, and point symbol is made. Additionally, the tiling patterns of the monolayered structures are deducted. We demonstrate that high-pressure metathesis offers a systematic access to rare-earth nitridophosphates with an atomic ratio of P/N between 1/2 and 1/4.

Average and local structure, debye temperature, and structural rigidity in some oxide compounds related to phosphor hosts.

The average and local structure of the oxides Ba2SiO4, BaAl2O4, SrAl2O4, and Y2SiO5 are examined to evaluate crystal rigidity in light of recent studies suggesting that highly connected and rigid structures yield the best phosphor hosts. Simultaneous momentum-space refinements of synchrotron X-ray and neutron scattering yield accurate average crystal structures, with reliable atomic displacement parameters. The Debye temperature ΘD, which has proven to be a useful proxy for structural rigidity, is extracted from the experimental atomic displacement parameters and compared with predictions from density functional theory calculations and experimental low-temperature heat capacity measurements. The role of static disorder on the measured displacement parameters, and the resulting Debye temperatures, are also analyzed using pair distribution function of total neutron scattering, as refined over varying distance ranges of the pair distribution function. The interplay between optimal bonding in the structure, structural rigidity, and correlated motion in these structures is examined, and the different contributions are delineated.