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1. Experimental and Theoretical Study on the Substitution Patterns in Lithium Germanides: The Case of Li 15 Ge 4 vs Li 14 ZnGe 4

   https://doi.org/10.1002/ejic.202100901  

   Osman, Hussien H. ; Bobev, Svilen ( December 2021 , European Journal of Inorganic Chemistry)

   A new ternary lithium zinc germanide, Li_13.83Zn_1.17(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 Li_15−xZn_xGe₄(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.

    

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2. Yet Another Case of Lithium Metal Atoms and Germanium Atoms Sharing Chemistry in the Solid State: Synthesis and Structural Characterization of Ba 2 LiGe 3

   https://doi.org/10.1002/chem.202302385  

   Ghosh, Kowsik ; Bobev, Svilen ( October 2023 , Chemistry – A European Journal)

   Several Ba−Li−Ge ternary phases are known and structurally characterized, including the title compound Ba₂LiGe₃. Its structure is reported to contain [Ge₆]¹⁰⁻anions that exhibit delocalized bonding with a Hückel‐like aromatic character. The Ge atoms are in the same plane with the Li atoms, and if both types of atoms are considered as covalently bonded, [LiGe₃]⁴⁻honeycomb‐like layers will result. The latter are separated by slabs of Ba²⁺cations. However, based on the systematic work detailed herein, it is necessary to re‐evaluate the phase as Ba₂Li_1−xGe_3+x(x<0.05). Although small, the homogeneity range is clearly demonstrated in the gradual change of the unit cell for four independent samples. Subsequent characterization by single‐crystal X‐ray diffraction methods shows that the Ba₂Li_1−xGe_3+xstructure, responds to the varied number of valence electrons and the changes are most pronounced for the refined lengths of the Li−Ge and Ge−Ge bonds. Indirectly, the changes in the Ge−Li/Ge distances within layers affect the stacking too, and these changes can be correlated to the variation of thec‐cell parameter. Chemical bonding analysis based on TB‐LMTO‐ASA level calculations affirms the notion for covalent character of the Ge−Ge bonds; the Ba−Ge and Li−Ge interactions also show some degree of covalency.

    

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3. Synthesis, crystal and electronic structure of BaLixCd13–x (x ≈ 2)

   https://doi.org/10.3389/fchem.2022.991625  

   Peng, Wanyue ; Baranets, Sviatoslav ; Bobev, Svilen ( September 2022 , Frontiers in Chemistry)

   A new ternary phase has been synthesized and structurally characterized. BaLi x Cd 13– x ( x ≈ 2) adopts the cubic NaZn 13 structure type (space group Fm 3 ¯ c , Pearson symbol cF 112) with unit cell parameter a = 13.5548 (10) Å. Structure refinements from single-crystal X-ray diffraction data demonstrate that the Li atoms are exclusively found at the centers of the Cd 12 -icosahedra. Since a cubic BaCd 13 phase does not exist, and the tetragonal BaCd 11 is the most Cd-rich phase in the Ba–Cd system, BaLi x Cd 13– x ( x ≈ 2) has to be considered as a true ternary compound. As opposed to the typical electron count of ca. 27 e -per formula unit for many known compounds with the NaZn 13 structure type, BaLi x Cd 13– x ( x ≈ 2) only has ca. 26 e -, suggesting that both electronic and geometric factors are at play. Finally, the bonding characteristics of the cubic BaLi x Cd 13– x ( x ≈ 2) and tetragonal BaCd 11 are investigated using the TB-LMTO-ASA method, showing metallic-like behavior. 

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4. Structural and Electronic Properties of Cu3InSe4

   https://doi.org/10.3390/cryst12091310  

   Ojo, Oluwagbemiga P. ; Wong-Ng, Winnie ; Chang, Tieyan ; Chen, Yu-Sheng ; Nolas, George S. ( September 2022 , Crystals)

   Single crystals of a new ternary chalcogenide Cu3InSe4 were obtained by induction melting, allowing for a complete investigation of the crystal structure by employing high-resolution single-crystal synchrotron X-ray diffraction. Cu3InSe4 crystallizes in a cubic structure, space group P4¯3m, with lattice constant 5.7504(2) Å and a density of 5.426 g/cm3. There are three unique crystallographic sites in the unit cell, with each cation bonded to four Se atoms in a tetrahedral geometry. Electron localization function calculations were employed in investigating the chemical bonding nature and first-principle electronic structure calculations are also presented. The results are discussed in light of the ongoing interest in exploring the structural and electronic properties of new chalcogenide materials. 

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5. Rare‐earth Metal Substitution in Calcium Germanides with the Tetragonal Cr 5 B 3 Type Structure

   https://doi.org/10.1002/zaac.202200183  

   Suen, Nian‐Tzu ; Bobev, Svilen ( July 2022 , Zeitschrift für anorganische und allgemeine Chemie)

   Calcium germanides with two mid‐late rare‐earth metals, Ca_5−xGd_xGe₃and Ca_5−xTb_xGe₃(x≈0.1−0.2), have been synthesized and structurally characterized. Additionally, a lanthanum‐rich germanide with calcium substitutions, La_5−xCa_xGe₃(x≈0.5) has also been identified. The three structures have been established from single‐crystal X‐ray diffraction methods and confirmed to crystallize with the Cr₅B₃‐type in the tetragonal space groupI4/mcm(no. 140;Z=4; Pearson symboltI32), where part of the germanium atoms are interconnected into Ge₂‐dimers, formally [Ge₂]⁶⁻. Rare‐earth metal and calcium atoms are arranged in distorted trigonal prisms, square‐antiprisms and cubes, centered by Ge or rare‐earth/calcium metal atoms. These studies show that the amount of trivalent rare‐earth metal atoms substituting divalent calcium atoms is in direct correlation with the lengths of the Ge−Ge bond within the Ge₂‐dimers, with distance varying between 2.58 Å in Ca_5−xGd_xGe₃and 2.75 Å in La_5−xCa_xGe₃. Such an elongation of the Ge−Ge bond is consistent with the notion that the parent Ca₅Ge₃Zintl phase (e. g. (Ca²⁺)₅[Ge₂]⁶⁻[Ge⁴⁻]) is being driven out of the ideal valence electron count and further reduced. In this context, this work demonstrates the ability of the germanides with the Cr₅B₃structure type to accommodate substitutions and wider valence electron count while maintaining their global structural integrity.

    

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