Purcell Jamie W, Miras Haralampos N, Long De-Liang, Markopoulou Panagiota, Cronin Leroy
WestCHEM School of Chemistry, University of Glasgow, Glasgow, G12 8QQ, UK.
Chemistry. 2017 Jul 18;23(40):9683-9689. doi: 10.1002/chem.201701920. Epub 2017 Jun 29.
The preparation and characterization of a new family of four polyoxothiometalate (POTM) clusters are reported, with varying size and complexity, based upon the dimeric [Mo O S (H O) ] cation with the general formula (NMe ) K [(Mo O S ) (TeO ) (C O ) (OH) ] where a,b,c,d,e,f={1,7,14,2,4,10}=1, {Mo Te }; {2,26,36,12,10,48}=2, {Mo Te }; {0,11,15,3,3,21}=3, {Mo Te }; {2,6,12,2,4,16}=4, {Mo Te }. The incorporation of tellurite anions allowed the fine tuning of the templating and bridging of the available building blocks, leading to new topologies of increased complexity. The structural diversity of this family of compounds ranges from the highly symmetrical cross-shaped {Mo Te } to the stacked ring structure of {Mo Te }, which is the largest tellurium-containing POTM cluster reported so far. Also a detailed experimental analysis revealed that the pH isolation window extends from acidic to basic values. ESI-MS analyses not only confirmed the stability of this family in solution but also revealed the stability of the observed virtual building blocks.
报道了四个新的多氧硫代金属酸盐(POTM)簇家族的制备与表征,它们基于二聚体[MoOS(H₂O)]阳离子,具有不同的尺寸和复杂性,通式为(NMe₄)₃K[(Mo₃O₉S₃)(TeO₃)ₐ(CO₃)ₑ(OH)ₓ],其中a、b、c、d、e、f={1,7,14,2,4,10}=1,{Mo₃Te₁};{2,26,36,12,10,48}=2,{Mo₆Te₂};{0,11,15,3,3,21}=3,{Mo₉Te₃};{2,6,12,2,4,16}=4,{Mo₁₂Te₄}。亚碲酸盐阴离子的引入使得对可用结构单元的模板化和桥连进行微调成为可能,从而产生了复杂度增加的新拓扑结构。该化合物家族的结构多样性范围从高度对称的十字形{Mo₃Te₁}到{Mo₁₂Te₄}的堆叠环结构,后者是迄今为止报道的最大的含碲POTM簇。此外,详细的实验分析表明,pH分离窗口从酸性值延伸到碱性值。电喷雾电离质谱(ESI-MS)分析不仅证实了该家族在溶液中的稳定性,还揭示了所观察到的虚拟结构单元的稳定性。