Botta Manuel, Zeitz Sabine, Klein Wilhelm, Raudaschl-Sieber Gabriele, Fässler Thomas F
Technical University of Munich (TUM), TUM School of Natural Sciences, Department of Chemistry, Chair of Inorganic Chemistry with Focus on New Materials, Lichtenbergstrasse 4, D-85748 Garching, Germany.
Technical University of Munich (TUM), TUM School of Natural Sciences, Department of Chemistry, Chair of Inorganic and Metal-Organic Chemistry, Lichtenbergstrasse 4, D-85748 Garching, Germany.
Inorg Chem. 2024 Oct 28;63(43):20108-20116. doi: 10.1021/acs.inorgchem.4c00287. Epub 2024 Apr 19.
Recently, ternary lithium phosphidotetrelates have attracted interest particularly due to their high ionic conductivities, while corresponding sodium and heavier alkali metal compounds have been less investigated. Hence, we report the synthesis and characterization of the novel ternary sodium phosphidogermanate NaGeP, which is readily accessible via ball milling of the elements and subsequent annealing. According to single crystal X-ray structure determination, NaGeP crystallizes in the monoclinic space group 2/ (no. 14.) with unit cell parameters of = 7.2894(6) Å, = 14.7725(8) Å, = 7.0528(6) Å, β = 106.331(6)° and forms an unprecedented two-dimensional polyanionic network in the plane of interconnected [PGe-GeP] building units. The system can also be interpreted as differently sized ring structures that interconnect and form a two-dimensional network. A comparison with related ternary compounds from the corresponding phase system as well as with the binary compound GeP shows that the polyanionic network of NaGeP resembles an intermediate step between highly condensed cages and discrete polyanions, which highlights the structural variety of phosphidogermanates. The structure is confirmed by Na- and P-MAS NMR measurements and Raman spectroscopy. Computational investigation of the electronic structure reveals that NaGeP is an indirect band gap semiconductor with a band gap of 2.9 eV.
最近，三元磷化物尤其因其高离子电导率而引起了人们的关注，而相应的钠及更重碱金属化合物的研究较少。因此，我们报道了新型三元磷锗酸钠NaGeP的合成与表征，它可通过元素球磨及后续退火轻松制备。根据单晶X射线结构测定，NaGeP以单斜空间群2/（编号14）结晶，晶胞参数为 = 7.2894(6) Å， = 14.7725(8) Å， = 7.0528(6) Å，β = 106.331(6)°，并在由相互连接的[PGe-GeP]结构单元构成的 平面内形成了前所未有的二维聚阴离子网络。该体系也可解释为不同尺寸的环状结构相互连接并形成二维网络。与相应相体系中的相关三元化合物以及二元化合物GeP的比较表明，NaGeP的聚阴离子网络类似于高度缩合笼状结构和离散聚阴离子之间的中间步骤，这突出了磷锗酸盐的结构多样性。通过Na和P的固体核磁共振测量以及拉曼光谱对结构进行了确认。电子结构的计算研究表明，NaGeP是一种间接带隙半导体，带隙为2.9 eV。
