Oxidation of Ge₉ Zintl clusters can afford condensed cluster species in the form of dimers, oligomers and polymers. In this work, we present a new route for the synthesis of Ge₉ tetramers present in the compound [K(18‐crown‐6)]₈[Ge₉=Ge₉=Ge₉=Ge₉] ⋅ 4 pyr. The reaction of a pyridine solution of K₄Ge₉ with 18‐crown‐6 first leads to the formation of green needles of yet unknown composition, which convert into the reported tetramer over time. In this reaction pyridine acts as oxidation reagent. Raman studies on the green needles as well as on tetrameric and polymeric Ge₉ feature complex vibrational patterns. Furthermore, we present the crystal structure of a new type of Ge₉ dimer in the compound K₄[K(2.2.2‐crypt)]₂[Ge₉−Ge₉] ⋅ 4 en ⋅ 2 thf, which represents an intermediate between the two established conformers.

中文翻译：

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[Ge9] 4-晶体结构的氧化和链接的Ge9团簇的拉曼光谱研究

Ge ₉ Zintl团簇的氧化可提供二聚体，低聚物和聚合物形式的缩合的团簇物种。在这项工作中，我们提出了一种合成存在于化合物[K（18-crown-6）] ₈ [Ge ₉ = Ge ₉ = Ge ₉ = Ge ₉ = Ge ₉ ]⋅4 pyr的Ge ₉四聚体的新途径。K ₄ Ge ₉的吡啶溶液与18-crown-6的反应首先导致形成绿色针状物，但其组成尚不明确，随着时间的推移会转化为四聚体。在该反应中，吡啶充当氧化剂。拉曼研究绿色针，四聚体和聚合Ge ₉具有复杂的振动模式。此外，我们介绍了化合物K ₄ [K（2.2.2-crypt）] ₂ [Ge ₉ -Ge ₉ ]⋅4 en⋅2 thf中新型Ge ₉二聚体的晶体结构，它表示介于这两个既定的构象者。