Extreme Differences in Oxidation States: Synthesis and Structural Analysis of the Germanide Oxometallates A10[Ge9]2[WO4] As Well As A10+x[

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• 作者：Viktor Hlukhyy ; Thomas F. F盲ssler ; Sim茅on Ponou ; Sven Lidin ; Natalia P. Ivleva ; Reinhard Niessner
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：April 2, 2012
• 年：2012
• 卷：51
• 期：7
• 页码：4058-4065
• 全文大小：416K
• 年卷期：v.51,no.7(April 2, 2012)
• ISSN：1520-510X

文摘

Semitransparent dark-red or ruby-red moisture- and air-sensitive single crystals of A_10+x[Ge₉]₂[W_1鈥?i>xNb_xO₄] (A = K, Rb; x = 0, 0.35) were obtained by high-temperature solid-state reactions. The crystal structure of the compounds was determined by single-crystal X-ray diffraction experiments. They crystallize in a new structure type (P2₁/c, Z = 4) with a = 13.908(1) 脜, b = 15.909(1) 脜, c = 17.383(1) 脜, and 尾 = 90.050(6)掳 for K_10.35(1)[Ge₉]₂[W_0.65(1)Nb_0.35(1)O₄]; a = 14.361(3) 脜, b = 16.356(3) 脜, c = 17.839(4) 脜, and 尾 = 90.01(3)掳 for Rb_10.35(1)[Ge₉]₂[W_0.65(1)Nb_0.35(1)O₄]; a = 13.8979(2) 脜, b = 15.5390(3) 脜, c = 17.4007(3) 脜, and 尾 = 90.188(1)掳 for K₁₀[Ge₉]₂WO₄; and a = 14.3230(7) 脜, b = 15.9060(9) 脜, c = 17.8634(9) 脜, and 尾 = 90.078(4)掳 for Rb₁₀[Ge₉]₂WO₄. The compounds contain discrete Ge₉^{4鈥?/sup> Wade鈥檚 nido clusters and WO₄2鈥?/sup> (or NbO₄3鈥?/sup>) anions, which are packed according to a hierarchical atom-to-cluster replacement of the Al₂Cu prototype and are separated by K and Rb cations, respectively. The alkali metal atoms occupy the corresponding tetrahedral sites of the Al₂Cu prototype. The amount of the alkali metal atoms on these diamagnetic compounds corresponds directly to the amount of W substituted by Nb. Thus, the transition metals W and Nb appear with oxidation numbers +6 and +5, respectively, in the vicinity of a [Ge₉]4鈥?/sup> polyanion. The crystals of the mixed salts were further characterized by Raman spectroscopy. The Raman data are in good agreement with the results from the X-ray structural analyses.}