Combining MN6 Octahedra and PN5 Trigonal Bipyramids in the Mica‐like Nitridophosphates MP6N11 (M=Al, In)

Ambach, Sebastian J.; Pointner, Monika; Falkai, Sophie; Paulmann, Carsten; Schnick, Wolfgang

doi:10.1002/anie.202303580

Cited by 7 publications

(1 citation statement)

References 51 publications

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“…Analogous to the isoelectronic combination of elements Si/O, forming SiO 4 tetrahedra, compounds mostly consist of PN 4 tetrahedra as basic structural building units. The tetrahedra can be found isolated, connected to small rings, chains, layers, or three-dimensional (3D) networks. − Interconnections of tetrahedra are mostly realized as vertex-sharing; however, edge-sharing has also been reported. − Besides PN 4 tetrahedra, PN 5 pyramids, either square based (e.g., in γ-P 3 N 5 ) or trigonal bipyramidal (e.g., in γ-HP 4 N 7 or M P 6 N 11 (M = Al, In)) are occasionally encountered. − Even PN 6 octahedra have been reported, e.g., in β-BP 3 N 6 at 42 GPa and δ-P 3 N 5 at 72 GPa. , This abundance of structural motifs leads to nitridophosphates finding use in a broad range of applications. For example, the binary phosphorus(V) nitride P 3 N 5 is used as a gate insulator in metal–insulator-semiconductor field-effect transistors (MISFETs) and was also investigated as a flame retardant or for safety in pyrotechnics. − The nitridic clathrate P 4 N 4 (NH) 4 (NH) 3 was discussed as a gas storage material .…”

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confidence: 99%

Building Nitridic Networks with Phosphorus and Germanium–from Ge^IIP₂N₄ to Ge^IVPN₃

Ambach,

Krach,

Bykova

et al. 2024

Inorg. Chem.

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Nitridophosphates and nitridogermanates attract high interest in current research due to their structural versatility. Herein, the elastic properties of GeP 2 N 4 were investigated by single-crystal X-ray diffraction (XRD) upon compression to 44.4(1) GPa in a diamond anvil cell. Its isothermal bulk modulus was determined to be 82(6) GPa. At 44.4(1) GPa, laser heating resulted in the formation of multiple crystalline phases, one of which was identified as unprecedented germanium nitridophosphate GePN 3 . Its structure was elucidated from single-crystal XRD data (C2/c (no. 15), a = 8.666( 5), b = 8.076(4), c = 4.691(2) Å, β = 101.00(7)°) and is built up from layers of GeN 6 octahedra and PN 4 tetrahedra. The GeN 6 octahedra form double zigzag chains, while the PN 4 tetrahedra are found in single zigzag chains. GePN 3 can be recovered to ambient conditions with a unit cell volume increase of about 12%. It combines P V and Ge IV in a condensed nitridic network for the first time.

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Section: Introductionmentioning

confidence: 99%

Building Nitridic Networks with Phosphorus and Germanium–from Ge^IIP₂N₄ to Ge^IVPN₃

Ambach,

Krach,

Bykova

et al. 2024

Inorg. Chem.

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Trigonal Planar [PN₃]⁴⁻ Anion in the Nitridophosphate Oxide Ba₃[PN₃]O

Pritzl,

Witthaut,

Dialer

et al. 2024

Angewandte Chemie

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Nitridophosphates, with their primary structural motif of isolated or condensed PN4 tetrahedra, meet many requirements for high performance materials. Their properties are associated with their structural diversity, which is mainly limited by this specific building block. Herein, we present the alkaline earth metal nitridophosphate oxide Ba3[PN3]O featuring a trigonal planar [PN3]4– anion. Ba3[PN3]O was obtained using a hot isostatic press by medium‐pressure high‐temperature synthesis (MP/HT) at 200 MPa and 880 °C. The crystal structure was solved and refined from single‐crystal X‐ray diffraction data in space group R‐3c (no.167) and confirmed by SEM‐EDX, magic angle spinning (MAS) NMR, vibrational spectroscopy (Raman, IR) and low‐cost crystallographic calculations (LCC). MP/HT synthesis reveals great potential by extending the structural chemistry of P to include trigonal planar [PN3]4– motifs.

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Adamantane‐Type Nitridophosphate Phosphors AE_xLi_10−2xP₄N₁₀ : Eu2⁺ via Medium‐Pressure Ion‐Exchange Reactions

Pritzl,

Buda,

Witthaut

et al. 2024

Angewandte Chemie

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Nitridophosphates have emerged as promising host compounds in the field of solid‐state lighting. Their industrial relevance has increased significantly, mainly due to recent advances in synthetic approaches under medium‐pressure (MP) conditions, including ammonothermal synthesis and hot isostatic pressing (HIP). In this study, we report on the synthesis and characterization of the quaternary representatives CaxLi10–2xP4N10 (x = 2, 2.7, 4) and Sr3Li4P4N10, prepared via a simplified ion exchange reaction under MP conditions, starting from the nitridophosphate‐based lithium ion conductor Li10P4N10. The synthesis route allowed for the preservation of the anionic [P4N10]10– structural motif of the starting material, while simultaneously introducing potential doping sites for Eu2+ by incorporating divalent alkaline earth cations (Ca2+/Sr2+). Upon excitation of Eu2+ doped samples with blue light, strong luminescence due to parity‐allowed 4f6(7F)5d1→4f7(8S7/2) transition can be observed in the red (Ca2Li6P4N10:Eu2+: λmax = 626 nm), yellow/orange (Ca2.7Li4.6P4N10:Eu2+: λmax1 = 506 nm, λmax2 = 592 nm and Sr3Li4P4N10:Eu2+: λmax = 596 nm) and green (Ca4Li2P4N10:Eu2+: λmax = 546 nm) spectral regions of the visible light. The compounds presented, together with the simplified synthetic approach, demonstrate the significant potential of ion exchange on Li ion conductors for the development of novel nitridophosphates in the future.

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Combining MN₆ Octahedra and PN₅ Trigonal Bipyramids in the Mica‐like Nitridophosphates MP₆N₁₁ (M=Al, In)

Cited by 7 publications

References 51 publications

Building Nitridic Networks with Phosphorus and Germanium–from Ge^IIP₂N₄ to Ge^IVPN₃

Building Nitridic Networks with Phosphorus and Germanium–from Ge^IIP₂N₄ to Ge^IVPN₃

Trigonal Planar [PN₃]⁴⁻ Anion in the Nitridophosphate Oxide Ba₃[PN₃]O

Adamantane‐Type Nitridophosphate Phosphors AE_xLi_10−2xP₄N₁₀ : Eu2⁺ via Medium‐Pressure Ion‐Exchange Reactions

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Combining MN6 Octahedra and PN5 Trigonal Bipyramids in the Mica‐like Nitridophosphates MP6N11 (M=Al, In)

Cited by 7 publications

References 51 publications

Building Nitridic Networks with Phosphorus and Germanium–from GeIIP2N4 to GeIVPN3

Building Nitridic Networks with Phosphorus and Germanium–from GeIIP2N4 to GeIVPN3

Trigonal Planar [PN3]4− Anion in the Nitridophosphate Oxide Ba3[PN3]O

Adamantane‐Type Nitridophosphate Phosphors AExLi10−2xP4N10 : Eu2+ via Medium‐Pressure Ion‐Exchange Reactions

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Combining MN₆ Octahedra and PN₅ Trigonal Bipyramids in the Mica‐like Nitridophosphates MP₆N₁₁ (M=Al, In)

Building Nitridic Networks with Phosphorus and Germanium–from Ge^IIP₂N₄ to Ge^IVPN₃

Building Nitridic Networks with Phosphorus and Germanium–from Ge^IIP₂N₄ to Ge^IVPN₃

Trigonal Planar [PN₃]⁴⁻ Anion in the Nitridophosphate Oxide Ba₃[PN₃]O

Adamantane‐Type Nitridophosphate Phosphors AE_xLi_10−2xP₄N₁₀ : Eu2⁺ via Medium‐Pressure Ion‐Exchange Reactions