Cover Feature: Experimental and Theoretical Study on the Substitution Patterns in Lithium Germanides: The Case of Li 15 Ge 4 vs Li 14 ZnGe 4 (Eur. J. Inorg. Chem. 4/2022)
Cover Feature: Experimental and Theoretical Study on the Substitution Patterns in Lithium Germanides: The Case of Li 15 Ge 4 vs Li 14 ZnGe 4 (Eur. J. Inorg. Chem. 4/2022)
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封面专题：锗化锂中取代模式的实验和理论研究：Li 15 Ge 4 与 Li 14 ZnGe 4 的案例（Eur. J. Inorg. Chem. 4/2022）
DOI：
10.1002/ejic.202200005
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发表时间：
2022
影响因子：
2.3
通讯作者：
Bobev, Svilen
中科院分区：
文献类型：
--
作者：
Osman, Hussien H.;Bobev, Svilen
通过高温固相反应合成了新的三元锂锌锗化合物Li13.83Zn1.17(2)Ge4。用单晶X射线衍射法测定了其晶体结构。新相为体心立方空间群I3d(NO.220)，晶胞参数为10.695(1)ä。晶体结构优化结果表明，Li15Ge4母体结构稳定为Li15−xZnxGe4(x≈1)，Li原子被富含单电子的锌原子随机取代，价电子数增加，体系电子更加稳定。通过理论和实验研究了母体Li15Ge4结构中的取代效应，证实了该结构中的锌原子优先占据Li的两个可用晶位中的一个。DFT电子结构计算支持由实验结果建立的优先取代模式，这也探索了标题化合物的化学键和电子性质的微妙之处。
A new ternary lithium zinc germanide, Li13.83Zn1.17(2)Ge4, was synthesized by a high‐temperature solid state reaction of the respective elements. The crystal structure was determined by single‐crystal X‐ray diffraction methods. The new phase crystallizes in the body‐centered cubic space groupI3d(no. 220) with unit cell parameter of 10.695(1) Å. The crystal structure refinements show that the parent Li15Ge4structure is stabilized as Li15−xZnxGe4(x≈1) via random substitution of Li atoms by the one‐electron‐richer atoms of the element Zn, by virtue of which the number of valence electrons increases, leading to a more electronically stable system. The substitution effects in the parent Li15Ge4structure were investigated through both theory and experiment, which confirm that the Zn atoms in this structure prefer to occupy only one of the two available crystallographic sites for Li. The preferred substitution pattern established from experimental results is supported by DFT electronic structure calculations, which also explore the subtleties of the chemical bonding and the electronic properties of the title compounds.