CaLi2PN3 - A Quaternary Chain-Type Nitridophosphate by Medium-Pressure Synthesis.

Nitridophosphates are in the focus of current research interest due to their structural versatility and properties, such as ion conductivity, ultra-incompressibility and luminescent properties when doped with suitable activator ions. Multinary representatives often require thorough investigation due to the competition with the thermodynamically more stable binary and ternary compounds. Another point of concern is the synthetic control of structural details, which is usually limited by conventional bottom-up syntheses. In this study, we report on the synthesis and characterization of the quaternary nitridophosphate CaLi2PN3. Various synthesis protocols were used for the preparation of CaLi2PN3, including the novel nitridophosphate double salt approach. The crystal structure was solved and refined from single-crystal X-ray diffraction data and confirmed by Rietveld refinement, solid-state NMR spectroscopy, EDX measurements and low-cost crystallographic calculations. The experimental results were corroborated by DFT calculations, which revealed the electronic band structure. Formation energy calculations allowed conclusions to be drawn about the stability in comparison to the initial ternary nitridophosphates. The synthesis of CaLi2PN3 exemplifies the enormous potential of medium-pressure syntheses in the field of nitridophosphate research. Furthermore, the presented new synthesis route allows a certain degree of structural control, which is a promising addition to previous synthesis strategies in nitridophosphate chemistry.

Synthesis of Nitride Zeolites in a Hot Isostatic Press.

The recently introduced nitridophosphate synthesis in a hot isostatic press (HIP) enabled simple access to large-scale product quantities starting from exclusively commercially available starting materials. Herein, we show that this method is suitable for the synthesis of highly condensed functional nitridophosphates, as well. Hence, the syntheses of the nitridophosphate zeolites Ba3 P5 N10 X (X=Cl, Br) are presented as proof of concept for this innovative access. Furthermore, samples of unprecedented Sr3 P5 N10 X (X=Cl, Br) were prepared and characterized to demonstrate the advantages of this synthetic approach over commonly used methods. Luminescence investigations on Eu2+ -doped samples of AE3 P5 N10 X (AE=Sr, Ba; X=Cl, Br) were carried out and characteristics of observed emission bands are discussed.

Crystalline Nitridophosphates by Ammonothermal Synthesis.

Nitridophosphates are a well-studied class of compounds with high structural diversity. However, their synthesis is quite challenging, particularly due to the limited thermal stability of starting materials like P3 N5 . Typically, it requires even high-pressure techniques (e.g. multianvil) in most cases. Herein, we establish the ammonothermal method as a versatile synthetic tool to access nitridophosphates with different degrees of condensation. α-Li10 P4 N10 , ß-Li10 P4 N10 , Li18 P6 N16 , Ca2 PN3 , SrP8 N14 , and LiPN2 were synthesized in supercritical NH3 at temperatures and pressures up to 1070 K and 200 MPa employing ammonobasic conditions. The products were analyzed by powder X-ray diffraction, energy dispersive X-ray spectroscopy, and FTIR spectroscopy. Moreover, we established red phosphorus as a starting material for nitridophosphate synthesis instead of commonly used and not readily available precursors, such as P3 N5 . This opens a promising preparative access to the emerging compound class of nitridophosphates.

Sr3 P3 N7 : Complementary Approach by Ammonothermal and High-Pressure Syntheses.

Nitridophosphates exhibit an intriguing structural diversity with different structural motifs, for example, chains, layers or frameworks. In this contribution the novel nitridophosphate Sr3 P3 N7 with unprecedented dreier double chains is presented. Crystalline powders were synthesized using the ammonothermal method, while single crystals were obtained by a high-pressure multianvil technique. The crystal structure of Sr3 P3 N7 was solved and refined from single-crystal X-ray diffraction and confirmed by powder X-ray methods. Sr3 P3 N7 crystallizes in monoclinic space group P2/c. Energy-dispersive X-ray and Fourier-transformed infrared spectroscopy were conducted to confirm the chemical composition, as well as the absence of NHx functionality. The optical band gap was estimated to be 4.4 eV using diffuse reflectance UV/Vis spectroscopy. Upon doping with Eu2+ , Sr3 P3 N7 shows a broad deep-red to infrared emission (λem =681 nm, fwhm≈3402 cm-1 ) with an internal quantum efficiency of 42 %.

Nitridophosphate-Based Ultra-Narrow-Band Blue-Emitters: Luminescence Properties of AEP8 N14 :Eu2+ (AE=Ca, Sr, Ba).

The nitridophosphates AEP8 N14 (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 CaP8 N14 and SrP8 N14 are isotypic. The space group Cmcm was confirmed by powder X-ray diffraction. The structure of BaP8 N14 (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. CaP8 N14 (λem =470 nm; fwhm=1380 cm-1 ) and SrP8 N14 (λem =440 nm; fwhm=1350 cm-1 ) can be classified as the first ultra-narrow-band blue-emitting Eu2+ -doped nitridophosphates. BaP8 N14 shows a notably broader blue emission (λem =417/457 nm; fwhm=2075/3550 cm-1 ).

BaP6 N10 NH:Eu2+ as a Case Study-An Imidonitridophosphate Showing Luminescence.

Barium imidonitridophosphate BaP6 N10 NH was synthesized at 5 GPa and 1000 °C with a high-pressure high-temperature approach using the multianvil technique. Ba(N3 )2 , P3 N5 and NH4 Cl were used as starting materials, applying a combination of azide and mineralizer routes. The structure elucidation of BaP6 N10 NH (P63 , a=7.5633(11), c=8.512(2) Å, Z=2) was performed by a combination of transmission electron microscopy and single-crystal diffraction with microfocused synchrotron radiation. Phase purity was verified by Rietveld refinement. 1 H and 31 P solid-state NMR and FTIR spectroscopy are consistent with the structure model. The chemical composition was confirmed by energy-dispersive X-ray spectroscopy and CHNS analyses. Eu2+ -doped samples of BaP6 N10 NH show blue emission upon excitation with UV to blue light (λem =460 nm, fwhm=2423 cm-1 ) representing unprecedented Eu2+ -luminescence of an imidonitride.

Post-Synthetic Modification: Systematic Study on a Simple Access to Nitridophosphates.

Nitridophosphates are a well-studied class of nitrides with diverse materials properties, such as luminescence or ion conductivity. Despite the growing interest in this compound class, their synthesis mostly works through direct combination of starting materials. Herein, we present a systematic study on a promising method for post-synthetic modification by treating pre-synthesized nitridophosphates with halides under elevated pressures and temperatures. Herein, we focus on the applicability of this approach to P/N compounds with different degrees of condensation. Accordingly, BaP2 N4 , Ba3 P5 N10 Br, SrH4 P6 N12 , CaP8 N14 , and Ca2 PN3 are investigated as model compounds for framework-, layer-, and chain-type nitridophosphates. The formation of structurally related, as well as, completely unrelated compounds, compared to the starting materials, shows the great potential of the approach, which increases the synthetic possibilities for nitridophosphates significantly.

HIP to be Square: Simplifying Nitridophosphate Synthesis in a Hot Isostatic Press.

(Oxo)Nitridophosphates have recently been identified as a promising compound class for application in the field of solid-state lighting. Especially, the latest medium-pressure syntheses under ammonothermal conditions draw attention of the semiconductor and lighting industry on nitridophosphates. In this contribution, we introduce hot isostatic presses as a new type of medium-pressure synthetic tool, further simplifying nitridophosphate synthesis. In a second step, phosphorus nitride was replaced as starting material by red phosphorus, enabling the synthesis of Ca2 PN3 as model compound, starting only from readily available compounds. Moreover, first luminescence investigations on Eu2+ -doped samples reveal Ca2 PN3 :Eu2+ as a promising broad-band red-emitter (λem =650 nm; fwhm=1972 cm-1 ). Besides simple handling, the presented synthetic method offers access to large sample volumes, and the underlying reaction conditions facilitate single-crystal growth, required for excellent optical properties.

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.

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.

SrH4 P6 N12 and SrP8 N14 : Insights into the Condensation Mechanism of Nitridophosphates under High Pressure.

The (imido)nitridophosphates SrH4 P6 N12 and SrP8 N14 were synthesized as colorless crystals by high-pressure/high-temperature reactions using the multianvil technique (5 GPa, ca. 1075 °C). Stoichiometric amounts of Sr(N3 )2, P3 N5 , and amorphous HPN2 were used as starting materials. Whereas the crystal structure of SrH4 P6 N12 was solved and refined from single-crystal X-ray diffraction data and confirmed by Rietveld refinement, the structure of SrP8 N14 was determined from powder diffraction data. In order to confirm the structures, 1 H and 31 P solid-state NMR spectroscopy and FTIR spectroscopy were carried out. The chemical composition was confirmed with EDX measurements. Both compounds show unprecedented layered network structure types, built up from all-side vertex-sharing PN4 tetrahedra which are structurally related. The structural comparison of both compounds gives first insights into the hitherto unknown condensation mechanism of nitridophosphates under high pressure.