Switchable High-Valent Ag <sup>3+</sup> /Ag <sup>+</sup> Redox Pair Stabilized in Polyoxometalate as Highly Oxidative “Electron Shuttle” Catalysts
We report the isolation and characterization of the first example of a crystallized high-valent Ag<sup>3+</sup>-containing polyoxometalate (POM) complex, Cs<sub>7</sub>K<sub>4</sub>[P<sub>2</sub>W<sub>19</sub>Ag<sup>III</sup>O<sub>69</sub>(OH<sub>2</sub>)]·17H<sub>2</sub>O (<b>1</b>), as a "catalyst bearing catalyst" capable of catalyzing the formation of the high-valent Ni<sup>3+</sup>-containing POMs in the presence of peroxydisulfate. The oxidation state and exotic chemical behaviors of Ag in <b>1</b> were confirmed by crystallographic, spectroscopic, and electrochemical characterizations. The Ag<sup>3+</sup>/Ag<sup>+</sup> redox pair embedded in <b>1</b> showed good electrochemical reversibility and the ability to accelerate electron transfer, contributing to the observed catalytic activity of <b>1</b> in both formation of other high-valent metal-containing POMs and electrochemical oxidative C-H activation.
Authors
- Hehua Hui (ORCID: https://orcid.org/0000-0002-0763-1636)
- Heyong He (ORCID: https://orcid.org/0000-0002-1781-6255)
- Yuanhang Ren (ORCID: https://orcid.org/0000-0002-7836-8847)
- Shik Chi Edman Tsang (ORCID: https://orcid.org/0000-0002-8796-3146)
- Xiang Li (ORCID: https://orcid.org/0000-0002-3782-2636)
- Yiyang Li (ORCID: https://orcid.org/0000-0002-9278-7386)
- Zhaoqing Liu (ORCID: https://orcid.org/0009-0007-8286-9090)
- Bin Yue (ORCID: https://orcid.org/0000-0001-7935-0684)
Institutions
- Peking University (CN)
- Fudan University (CN)
- University of Oxford (GB)
Publication Details
- Journal
- JACS Au
- Published
- 2025-10-14
- DOI
- https://doi.org/10.1021/jacsau.5c00987
- Citations
- 1
- Primary Topic
- Polyoxometalates: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 0.52