Solvothermal synthesis of a bimetallic thiometallate containing germanium in two oxidation states
Solvothermal synthesis of a bimetallic thiometallate containing germanium in two oxidation states
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DOI：
10.1016/j.jssc.2011.09.032
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发表时间：
2011-12
影响因子：
3.3
通讯作者：
A. Powell;Rosalyn Mackay
中科院分区：
文献类型：
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作者：
A. Powell;Rosalyn Mackay
在溶剂热条件下，在乙二胺存在下，在463K温度下制备了一种新的层状锗锑硫化物[Ge(C2N2H8)3][GeSb2S6]。该化合物已通过单晶x射线衍射、热重、元素分析和反射光谱进行了表征。[Ge(C2N2H8)3][GeSb2S6]在Pbca空间群中结晶(a=13.3284(5), b=17.4801（6), c=18.5447(7)Å）。该结构由环状[GeSb2S8]6 -单元组成，这些单元通过sb2s2环交联，形成化学计量[GeSb2S6]2 -层，其中有[Ge(en)3]2+阳离子。[Ge(C2N2H8)3][GeSb2S6]含有二价和四价锗。2.49(4)eV的光学带隙与先前确定的硫锑酸盐金属中心密度的相关性所期望的值非常一致，并且与价带顶部的态主要是硫3p特征相一致。
A new layered germanium–antimony sulphide, [Ge(C2N2H8)3][GeSb2S6], has been prepared at 463K under solvothermal conditions in the presence of ethylenediamine. The compound has been characterised by single-crystal X-ray diffraction, thermogravimetry, elemental analysis and reflectance spectroscopy. [Ge(C2N2H8)3][GeSb2S6] crystallises in the space group Pbca (a=13.3284(5), b=17.4801(6), c=18.5447(7)Å). The structure consists of cyclic [GeSb2S8]6−units that form chains which are cross-linked through Sb2S2rings to generate layers of stoichiometry [GeSb2S6]2−, between which [Ge(en)3]2+cations are located. [Ge(C2N2H8)3][GeSb2S6] contains germanium in both the divalent and tetravalent states. The optical band gap of 2.49(4)eV is in excellent agreement with the value expected on the basis of the correlation with the density of metal centres previously identified for thioantimonates, and is consistent with states at the top of the valence band being predominantly of sulphur 3p character.