Cover Picture: “Half‐Bonds” in an Unusual Coordinated S42− Rectangle (Chem. Asian J. 2/2009)

This stone lantern is known as the “Koto‐ji”, or “harp‐tuner”, as it resembles the tuning bridge of the Japanese koto. The six windows of the lantern are said to symbolize the six essential attributes of a perfect garden, such as the one it overlooks: spaciousness, seclusion, artifice, antiquity, abundant water, and broad views. R. Hoffmann et al. report on two synthesized compounds containing the unusual S₄^2? rectangles bound to either Ir or Rh fragments, illuminated by the two lamp windows. Like the Koto‐ji lantern, this paper, which suggests the presence of S? S half‐bonds, sheds some light in the garden of beautiful compounds. For more information, see their Full Paper on page 302 ff .

     

Structural Transformation with “Negative Volume Expansion”: Chemical Bonding and Physical Behavior of TiGePt

The synthesis and a joint experimental and theoretical study of the crystal structure and physical properties of the new ternary intermetallic compound TiGePt are presented. Upon heating, TiGePt exhibits an unusual structural phase transition with a huge volume contraction of about 10 %. The transformation is characterized by a strong change in the physical properties, in particular, by an insulator–metal transition. At temperatures below 885 °C TiGePt crystallizes in the cubic MgAgAs (half‐Heusler) type (LT phase, space group F$\bar 4$ 3m, a=5.9349(2) Å). At elevated temperatures, the crystal structure of TiGePt transforms into the TiNiSi structure type (HT phase, space group Pnma, a=6.38134(9) Å, b=3.89081(5) Å, c=7.5034(1) Å). The reversible, temperature‐dependent structural transition was investigated by in‐situ neutron powder diffraction and dilatometry measurements. The insulator–metal transition, indicated by resistivity measurements, is in accord with band structure calculations yielding a gap of about 0.9 eV for the LT phase and a metallic HT phase. Detailed analysis of the chemical bonding in both modifications revealed an essential change of the Ti–Pt and Ti–Ge interactions as the origin of the dramatic changes in the physical properties.