Hydrothermal Synthesis of Two Cationic Bismuthate Clusters: An Alkylenedisulfonate Bridged Hexamer, [Bi6O4(OH)4(H2O)2][(CH2)2(SO3)2]3 and a Rare Nonamer Templated by Triflate, [Bi9O8(OH)6][CF3SO3]5

This paper reports the synthesis, characterization, and application of two cationic bismuthate clusters by anion templating. The compounds were synthesized under mild hydrothermal treatment and characterized by powder and single-crystal X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The first material consists of a cationic hexanuclear bismuthate cluster octahedral in geometry and linked by 1,2-ethanedisulfonate molecules. This structure is thermally stable to about 235 °C. In the second compound, discrete cationic nonanuclear bismuthate clusters interact electrostatically with trifluoromethanesulfonate anions to pack into a nearly layered assembly. The material undergoes a transformation to Bi2O3 upon loss of the triflate groups at about 385 °C. Both materials demonstrate the use of sulfonate groups for the anion-directed assembly of these rare cationic inorganic structures. The application of the 3D octahedral bismuth cluster material toward acidic heterogeneous catalysis is also reported.

本文报告了通过阴离子模板法制备两种阳离子铋酸盐簇的合成、表征及其应用。这些化合物在温和的溶剂热处理条件下合成，并通过粉末和单晶X射线衍射、红外光谱和热重分析进行表征。第一种材料由八面体几何形状的阳离子六核铋酸盐簇组成，由1,2-乙二磺酸分子连接。该结构在约235°C时具有良好的热稳定性。在第二种化合物中，离散的阳离子九核铋酸盐簇通过静电相互作用与三氟甲磺酸根离子相互作用，形成一个近乎层状的结构。当在约385°C时失去三氟甲磺酸基团后，该材料发生转化，形成Bi2O3。这两种材料均展示了磺酸基团在阴离子导向组装这些稀有阳离子无机结构中的应用。此外，还报道了三维八面体铋簇材料在酸性非均相催化中的应用。