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WBeN和WBeN中环境和高温氮化铍基序的组合。

Combination of Ambient and High-Temperature Beryllium Nitride Motifs in WBeN and WBeN.

作者信息

Krach Georg, Werhahn Dominik, Witthaut Kristian, Johrendt Dirk, Schnick Wolfgang

机构信息

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

出版信息

Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202420583. doi: 10.1002/anie.202420583. Epub 2024 Nov 26.

Abstract

Compounds of transition metals and beryllium have a wide range of applications, from everyday tools to high tech applications. Remarkably, no single ternary beryllium nitride with a transition metal is known. Here, we report on the synthesis and properties of the first transition metal nitridoberyllates, namely WBeN and WBeN. Both compounds were synthesized in a high-temperature high-pressure approach from BeN and W, using azide generated N as an oxidizing agent. The crystal structures, consisting of alternating layers of WN trigonal prisms and BeN tetrahedra, were elucidated by single-crystal X-ray diffraction (sc-XRD). The separating nitridoberyllate layers show either ambient temperature (α-BeN type) or high temperature (β-BeN type) motifs. WBeN was further corroborated by infrared (IR), nuclear magnetic resonance (NMR) and UV/Vis spectroscopy and vibrating sample magnetometry (VSM) measurements. The latter revealed a mixed valence with an intermediate oxidation state of 3.5 for the W atoms. Both, the synthesis of the first transition metal nitridoberyllates and the synthesis approach using elemental W pave the way to a new field of nitride chemistry.

摘要

过渡金属与铍的化合物有着广泛的应用,从日常工具到高科技应用。值得注意的是,目前还没有已知的单一过渡金属三元氮化铍。在此,我们报道了首例过渡金属氮铍酸盐WBeN和WBeN的合成及性质。这两种化合物都是在高温高压条件下,以BeN和W为原料,利用叠氮化物产生的N作为氧化剂合成的。通过单晶X射线衍射(sc-XRD)确定了其晶体结构,该结构由WN三角棱柱和BeN四面体的交替层组成。分隔的氮铍酸盐层呈现出室温(α-BeN型)或高温(β-BeN型)结构单元。通过红外(IR)、核磁共振(NMR)、紫外/可见光谱以及振动样品磁强计(VSM)测量进一步证实了WBeN的性质。VSM测量表明W原子具有混合价态,中间氧化态为3.5。首例过渡金属氮铍酸盐的合成以及使用元素W的合成方法为氮化物化学的新领域开辟了道路。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0362/11795704/f175b50cdb2f/ANIE-64-e202420583-g006.jpg

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