Lin Qisheng, Corbett John D
Department of Chemistry, Iowa State University, Ames, Iowa 50010, USA.
Inorg Chem. 2007 Oct 15;46(21):8722-7. doi: 10.1021/ic700995e. Epub 2007 Sep 20.
The title compound, Ca(4)Au(10)In(3) (e/a = 1.59), was synthesized by conventional high-temperature solid-state reactions and structurally analyzed by single-crystal X-ray diffraction: space group Cmca, a = 13.729(4) A, b = 10.050(3) A, c = 10.160(3) A, Z = 4. The structure, isotypic with that of Zr(7)Ni(10), features a novel three-dimensional [Au(10)In(3)] polyanionic framework built from sinusoidal Au layers that are interconnected by significant Au-Au and Au-In interactions. A prominent electronic feature is the presence of a pseudogap and empty bonding states above the Fermi level according to LMTO calculations, reminiscent of the tunable electronic properties discovered for Mg(2)Zn(11)-type phases. The natures of the chemical and electronic redistributions from Zr(7)Ni(10) to Ca(4)Au(10)In(3) are considered. The Au backbone appears to be particularly important.
标题化合物Ca(4)Au(10)In(3)（电子/原子比e/a = 1.59）通过传统高温固态反应合成，并通过单晶X射线衍射进行结构分析：空间群Cmca，a = 13.729(4) Å，b = 10.050(3) Å，c = 10.160(3) Å，Z = 4。该结构与Zr(7)Ni(10)的结构同型，其特征是由正弦形金层构建的新型三维[Au(10)In(3)]聚阴离子骨架，这些金层通过显著的金-金和金-铟相互作用相互连接。根据LMTO计算，一个突出的电子特征是在费米能级以上存在一个赝能隙和空的成键态，这让人想起在Mg(2)Zn(11)型相中发现的可调电子性质。考虑了从Zr(7)Ni(10)到Ca(4)Au(10)In(3)的化学和电子重新分布的性质。金骨架似乎特别重要。
