Nickel-p-block metal mixed chalcogenides based on AuCu3-type fragments: Iodine-assisted synthesis as a way of obtaining new structures

Two new mixed nickel-gallium chalcogenides, Ni9.39Ga2S2 and Ni5.80GaTe2, and a new mixed nickel-indium telluride, Ni5.78InTe2, have been synthesized by a high-temperature ampoule route with the addition of iodine, and characterized from single-crystal or powder diffraction data. They belong to the relatively uncommon Ni7-xMQ2/Ni10-xM2Q2 type of structures (M = Ge, Sn, Sb, In), and are built from p-block metal-centered nickel cuboctahedra, alternating along the c axis with defective Cu2Sb-type nickel-chalcogen ones. Both tellurium-containing compounds show a small degree of orthorhombic distortion with respect to the idealized tetragonal structure, only detectable in the powder diffraction data. No phase transition to the tetragonal structure was detected for Ni5.80GaTe2 by the in situ powder diffraction measurements from room temperature to 550 °C. DFT calculations show close relationships of electronic structures of these ternary compounds to their parent intermetallics, Ni3M (M = Ga, In). Metallic conductivity and paramagnetic properties are predicted for all three with the latter confirmed by magnetic measurements. The bonding patterns, investigated via the ELF topological analysis, show multi-centered nickel-p-block metal bonds in the AuCu3-type fragments and pairwise covalent interactions in the nickel-chalcogen fragments. Both Ni7-xMTe2 compounds showed no structural or compositional changes upon high-temperature mid-pressure hydrogenation. This journal is © The Royal Society of Chemistry.

Stroganova E.A.1 , Kazakov S.M.1 , Efimov N.N.2 , Khrustalev V.N. 3 , Keilholz S.4 , Götze A.4 , Kohlmann H.4 , Kuznetsov A.N. 1, 2
Royal Society of Chemistry
Номер выпуска
  • 1 Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1-3 GSP-1, Moscow, 119991, Russian Federation
  • 2 N.S. Kurnakov Institute of General and Inorganic Chemistry, Ras, Leninsky pr. 31 GSP-1, Moscow, 119991, Russian Federation
  • 3 Joint Institute for Chemical Research, Rudn University, Miklukho-Maklaya str.6, Moscow, 117198, Russian Federation
  • 4 Inorganic Chemistry, Faculty for Chemistry and Mineralogy, Leipzig University, Johannisallee 29, Leipzig, 04103, Germany
Ключевые слова
Chalcogenides; Diffraction; Electronic structure; Gallium compounds; Indium compounds; Iodine; Metals; Nickel compounds; Powder metals; Single crystals; Tellurium compounds; Topology; Compositional changes; Covalent interactions; Metallic conductivity; Orthorhombic distortion; Paramagnetic properties; Situ powder diffractions; Tetragonal structure; Topological analysis; Sulfur compounds
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