American Chemical Society
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Different Cation Arrangements in Au−In Networks. Syntheses and Structures of Six Intermetallic Compounds in Alkali-Metal−Au−In Systems

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posted on 2007-07-23, 00:00 authored by Bin Li, John D. Corbett
Six robust intermetallic compounds with cations in three different tunnel-like structures have been synthesized in alkali-metal−Au−In systems via high-temperature solid-state methods and characterized by X-ray diffraction:  AAu4In6 [A = K (I), Rb (II), Pm2, Z = 1], K1.76(6)Au6In4 (III, I4/mcm, Z = 4), and AxAu2In2 [x ≈ 0.7, A = K (IV), Rb (V), Cs (VI), P42/nmc, Z = 8]. The first type is constructed from a single cage unit:  an alkali-metal-centered 21-vertex polyhedron A@Au9In12 with 6-9-6 arrangement of planar rings. The others contain uniaxial arrays of tunnels built of differently puckered eight- and four-member Au/In rings. The largely different cation distributions depend on the tunnel constitutions and cation sizes. Tight-binding electronic structure calculations by linear muffin-tin-orbital (LMTO) methods were performed for I and idealized III in order to help understand their chemical bonding. These also reveal large differences in relativistic effects for Au d orbitals, as well as for different Au sites in each structure.