Makin Sarah, Vaqueiro Paz
Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6DX, UK.
Molecules. 2021 Sep 6;26(17):5415. doi: 10.3390/molecules26175415.
Large discrete supertetrahedral clusters of metal chalcogenides are rare due to the difficulty of crystallizing solids in which the negative charge of the cluster is balanced by the positive charges of the countercations. Here, we describe a discrete ligand-free T3 supertetrahedral cluster, [GaS(SH)], which was successfully synthesized in the presence of the superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) using the neutral surfactant polyethyleneglycol (PEG)-400 as the reaction solvent. Protonated DBUH cations are incorporated into the crystal structure of the product, which can be formulated as [CHN][GaS(SH)]. This compound, which represents the first example of a discrete ligand-free T3 cluster of gallium sulfide, was fully characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis, and ultraviolet-visible diffuse reflectance. The results presented here indicate that the use of surfactants as solvents offers potential for the preparation of new compounds containing supertetrahedral clusters.
由于难以使固体结晶，其中簇的负电荷由抗衡阳离子的正电荷平衡，所以大的离散超四面体金属硫族化物簇很少见。在此，我们描述了一种离散的无配体T3超四面体簇[GaS(SH)]，它是在超强碱1,8 - 二氮杂双环[5.4.0]十一碳 - 7 - 烯（DBU）存在下，使用中性表面活性剂聚乙二醇（PEG）- 400作为反应溶剂成功合成的。质子化的DBUH阳离子被纳入产物的晶体结构中，其可被表述为[CHN][GaS(SH)]。该化合物代表了离散的无配体硫化镓T3簇的首个实例，通过单晶和粉末X射线衍射、元素分析、红外光谱、热重分析以及紫外 - 可见漫反射进行了全面表征。此处呈现的结果表明，使用表面活性剂作为溶剂为制备含超四面体簇的新化合物提供了潜力。
