K23Au12Sn9-An Intermetallic Compound Containing a Large Gold-Tin Cluster: Synthesis, Structure, and Bonding

TitleK23Au12Sn9-An Intermetallic Compound Containing a Large Gold-Tin Cluster: Synthesis, Structure, and Bonding
Publication TypeJournal Article
Year of Publication2010
AuthorsLi B, Kim SJ, Miller GJ, Corbett JD
Journal TitleInorganic Chemistry
Date Published02/15
ISBN Number0020-1669
Accession NumberISI:000274240700039
Keywordsbuilding-blocks, chemistry, crystal-structure, framework structure, germanium, metals, phases, polyhedra, solid-state, zintl-compounds

A polyanionic unit {Au12Sn9} with a novel "corrugated sheet" shape occurs in K23Au12Sn9. The compound was obtained by fusion of the pure elements in tantalum ampules at high temperatures followed by programmed cooling, and the structure was determined by X-ray diffraction: /(4) over bar 2m (No. 121), a = 20.834(3), c = 6.818(1) angstrom, Z= 2. The large heteroatomic cluster has D-2d point symmetry and features a central four bonded (4b-) Sri, eight 3b- or 2b-Sn on the perimeter, and 24 linking nearly linear Sn-Au bonds at 12 Au atoms. Formula splitting according to the Zintl concept suggests that the compound is one electron deficient, and linear muff in-tin-orbital (LMTO) electronic structure calculations show that the Fermi level (E-F) lies near a band gap at around 0.5 eV, that is, an incompletely filled valence band in concert with favorable atom packing. Large relative -ICOHP values for Au-Sn are consistent with the observed maximization of the number of heteroatomic bonds, whereas the numerous K-Sn and K-Au contacts contribute similar to 40% of the total -ICOHP. Extended-Huckel population and molecular orbital analyses indicate that the open band feature originates from 5p states that are associated with the 2b-corner Sri atoms. In accord with the electronic structure calculations, magnetic susceptibility measurements show a nearly temperature-independent paramagnetic property.

URL<Go to ISI>://000274240700039
DOIDoi 10.1021/Ic901771x