Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
Helmholtz Institute Ulm (HIU), Helmholtzstraße 11, 89081, Ulm, Germany.
Chemistry. 2021 Sep 20;27(53):13435-13441. doi: 10.1002/chem.202102352. Epub 2021 Aug 6.
Polyoxometalates (POMs) have emerged as material of interest in many applications such as energy storage and conversion due to their redox activity and molecularly defined structure. However, especially for polyoxovanadates a lack of understanding between structural modifications and physicochemical properties remains. The present study leverages a lacunary dodecavanadate to systematically investigate the electronic effect of heterometal functionalization. While structural distortion affects the stability of the cluster, the redox potentials correlate with the overall cluster charge. Furthermore, we report the first bromide-templated analogue of this cluster family. While the halide anion is crucial for the formation of the cluster, no major effect on the electrochemical properties is observed. By improving the understanding of structure-property relationship in this work, we hope to enable a more predictable tuning of redox-properties of polyoxovandates.
多金属氧酸盐（POMs）由于其氧化还原活性和分子定义的结构，在储能和转化等许多应用中成为人们关注的材料。然而，特别是对于多聚钒酸盐，结构修饰和物理化学性质之间的理解仍然缺乏。本研究利用一个缺位十二钒酸盐来系统地研究杂金属功能化的电子效应。虽然结构变形会影响簇的稳定性，但氧化还原电位与簇的总电荷相关。此外，我们还报道了该簇家族的首例溴化物模板类似物。虽然卤化物阴离子对于簇的形成至关重要，但对电化学性质没有观察到重大影响。通过提高对这项工作中结构-性质关系的理解，我们希望能够更准确地调节多聚钒酸盐的氧化还原性质。
