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云母的氮化物类似物AESiP₅N₈(AE = Mg、Mg₁₋ₓCaₓ、Ca、Sr)

Nitridic Analogs of Micas AESi P N (NH) (AE=Mg, Mg Ca , Ca, Sr).

作者信息

Eisenburger Lucien, Strobel Philipp, Schmidt Peter J, Bräuniger Thomas, Wright Jonathan, Bright Eleanor Lawrence, Giacobbe Carlotta, Oeckler Oliver, Schnick Wolfgang

机构信息

Department of Chemistry, University of Munich, Butenandtstraße 5-13, 81377, Munich, Germany.

Lumileds Phosphor Center Aachen (LPCA), Lumileds (Germany) GmbH, Philipsstraße 8, 52068, Aachen, Germany.

出版信息

Angew Chem Int Ed Engl. 2022 Jan 21;61(4):e202114902. doi: 10.1002/anie.202114902. Epub 2021 Dec 10.

Abstract

We present the first nitridic analogs of micas, namely AESi P N (NH) (AE=Mg, Mg Ca , Ca, Sr), which were synthesized under high-pressure high-temperature conditions at 1400 °C and 8 GPa from the refractory nitrides P N and Si N , the respective alkaline earth amides, implementing NH F as a mineralizer. The crystal structure was elucidated by single-crystal diffraction with microfocused synchrotron radiation, energy-dispersive X-ray spectroscopic (EDX) mapping with atomic resolution, powder X-ray diffraction, and solid-state NMR. The structures consist of typical tetrahedra-octahedra-tetrahedra (T-O-T) layers with P occupying T and Si occupying O layers, realizing the rare motif of sixfold coordinated silicon atoms in nitrides. The presence of H, as an imide group forming the SiN (NH) octahedra, is confirmed by SCXRD, MAS-NMR, and IR spectroscopy. Eu -doped samples show tunable narrow-band emission from deep blue to cyan (451-492 nm).

摘要

我们展示了云母的首个氮化物类似物,即AESiP₃N₅(NH)₂(AE = Mg、Mg₀.₅Ca₀.₅、Ca、Sr),它们是在1400 °C和8 GPa的高压高温条件下,由难熔氮化物P₃N₅和Si₃N₄、相应的碱土金属酰胺,并使用NH₄F作为矿化剂合成的。通过微聚焦同步辐射单晶衍射、原子分辨率的能量色散X射线光谱(EDX)映射、粉末X射线衍射和固态NMR对晶体结构进行了阐明。这些结构由典型的四面体-八面体-四面体(T-O-T)层组成,其中P占据T层,Si占据O层,实现了氮化物中六重配位硅原子这一罕见结构单元。通过单晶X射线衍射(SCXRD)、魔角旋转核磁共振(MAS-NMR)和红外光谱证实了H以形成SiN₂(NH)八面体的酰亚胺基团形式存在。Eu掺杂样品显示出从深蓝到青绿色(451 - 492 nm)的可调谐窄带发射。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d5c7/9300002/0a6a9d1253fd/ANIE-61-0-g002.jpg

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