A Mixed-Addenda Mo/W Organofunctionalised Hybrid Polyoxometalate
A Mixed-Addenda Mo/W Organofunctionalised Hybrid Polyoxometalate
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DOI：
10.1002/ejic.202200019
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发表时间：
2022-03-10
影响因子：
2.3
通讯作者：
Newton, Graham N.
中科院分区：
文献类型：
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作者：
Amin, Sharad S.;Cameron, Jamie M.;Newton, Graham N.
带有MO杂化聚体聚盐簇的混合添加剂-K-6 [P2W15MO2O61（POC6H5）（2）]（1）（1）在酸性条件下从K-10 [P2W15MO2O61]和PO3C6H7的凝结中合成。单晶X射线衍射证实了杂种簇的结构，并在腔簇的盖上存在两个mo中心。通过循环伏安法，光谱电子化学和电子顺磁共振光谱研究了金属取代的电子效应，并由密度功能理论计算支持。将1与仅钨模拟K-6 [P2W17O61（POC6H5）（2）]（2）进行比较，首次还原过程的更积极的潜力是由W替换W对MO的更积极的潜力，与群集Lumo能量的显着降低一致。
A mixed-addenda W/Mo hybrid polyoxometalate cluster - K-6[P2W15Mo2O61(POC6H5)(2)] (1) was synthesised from the condensation of K-10[P2W15Mo2O61] and PO3C6H7 under acidic conditions. Single-crystal X-ray diffraction confirmed the structure of the hybrid cluster and the presence of two Mo centres in the cap of the lacunary cluster. The electronic effects of metal substitution were studied by cyclic voltammetry, spectroelectrochemistry and electron paramagnetic resonance spectroscopy and supported by density functional theory calculations. Comparing 1 to its tungsten-only analogue K-6[P2W17O61(POC6H5)(2)] (2), a more positive potential for the first reduction process was induced by the substitution of W for Mo, consistent with a significant lowering of the cluster LUMO energy.