Ni5.73InSe2 - a Metal-Rich Selenide Based on the Cu3Au-Type 2D Heterometallic Framework: Synthesis, Structure, and Bonding

作者：Kuznetsov Alexey N^*; Serov Alexey A

来源：European Journal of Inorganic Chemistry, 2016, 2016(3): 373-379.

DOI：10.1002/ejic.201501197

• Heterometallic complexes
• Metal-rich compounds
• Indium
• Nickel
• Selenium
• Chalcogens
• Density functional calculations

A new metal-rich nickel-indium selenide, Ni5.73InSe2, was synthesized by annealing a mixture of the elements with a 6: 1: 2 ratio at 650 degrees C for 7 days with subsequent cooling to room temperature. Its crystal structure was determined from singlecrystal diffraction data, and the composition confirmed by an EDS analysis. The compound crystallizes in the tetragonal system [I4/mmm, a = 3.6797(5) angstrom, c = 18.845(4) angstrom, Z = 2] and is isotypic with the Ni(7-x)MQ(2) phases (M = Si, Ge, Sn, Sb; Q = S, Se, Te). Its main structural units are indium- centered [Ni12In] cuboctahedra of the Cu3Au type and [Ni4-xSe2] blocks of the Cu2Sb type, alternating along the c axis. Electronic structure calculations on the DFT/FP-LAPW level predict metallic properties and indicate a temperature-independent paramagnetic behavior for the new compound, which is supported by the experimental measurements. The ELI-D topological analysis shows the multi- centered nature of the bonding in both the nickelindium and nickel- selenium fragments. Ni5.73InSe2 represents the first example of a quasi-2D mixed nickel- group 13 metal chalcogenide featuring [Ni12M] cuboctahedra of the Cu3Au type.

• 出版日期2016-1