Raabe Jan-Christian, Albert Jakob, Poller Maximilian J
Institute of Technical and Macromolecular Chemistry, Hamburg University, Bundesstrasse 45, 20146, Hamburg, Germany.
Chemistry. 2022 Sep 1;28(49):e202201084. doi: 10.1002/chem.202201084. Epub 2022 Jul 13.
Adjusting the RedOx activity of polyoxometalate catalysts is a key challenge for the catalysis of selective oxidation reactions. For this purpose, the possibility of influencing the RedOx potential by the introduction of an additional RedOx-active element was investigated. Thereby, Keggin-type polyoxometalates (POMs) with up to three different elements in the metal framework were created. An advanced and reproducible synthetic procedure to incorporate Mn and additionally V into Keggin-type heteropolyacids alongside comprehensive characterization of the new molecules is presented. The success of our syntheses was confirmed by vibrational spectroscopy (IR and Raman) and elemental analysis. Furthermore, the new compounds were analyzed by NMR spectroscopy to investigate the characteristics of the POMs in solution. The structures of successfully crystalized compounds were determined by single-crystal X-ray diffraction. Moreover, all synthesized compounds were characterized using UV/Vis spectroscopy and electrochemical analysis to get further insights into the electronic transfer processes and redox potentials.
调节多金属氧酸盐催化剂的氧化还原活性是选择性氧化反应催化中的一项关键挑战。为此，研究了通过引入额外的氧化还原活性元素来影响氧化还原电位的可能性。由此，制备了金属骨架中含有多达三种不同元素的Keggin型多金属氧酸盐（POMs）。本文介绍了一种先进且可重复的合成方法，用于将Mn以及V引入Keggin型杂多酸中，并对新分子进行全面表征。通过振动光谱（红外和拉曼）和元素分析证实了我们合成的成功。此外，通过核磁共振光谱对新化合物进行分析，以研究溶液中POMs的特性。通过单晶X射线衍射确定成功结晶化合物的结构。此外，使用紫外/可见光谱和电化学分析对所有合成化合物进行表征，以进一步深入了解电子转移过程和氧化还原电位。
