Covalently modified polyoxometalates (POMs), which benefit from the synergistic effect between POMs and covalently grafted moieties, have received increasing attention in various fields. Recent studies on the covalently modified POMs mainly focus on the function-directed POMs assemblies. In this review, we summarized the latest progress (2017-2022) of covalently modified POMs from functional perspective, which can be classified as assembly chemistry, photochemistry, electrochemistry, homogeneous/heterogeneous catalysis and biological application.The roles of POMs and covalently grafted moieties in these hybrids, especially the rational design for the specific application were considered and emphasized.

The Anderson-type polyoxometalates (POMs) are one of the most important and widely developed groups of the POMs family. The covalent functionalization of Anderson POMs have attracted extensive attention and facilitated...

Prion disorders are a group of lethal infectious neurodegenerative diseases caused by the spontaneous aggregation of misfolded prion proteins (PrPSc). The oxidation of such proteins by chemical reagents can significantly modulate their aggregation behavior. Herein, we exploit a series of vanadium-substituted Keggin-type tungsten and molybdenum POMs (W- and Mo-POMs) as chemical tools to oxidize PrP106–126 (denoted as PrP), an ideal model for studying PrPSc. Due to the band gaps being larger than that of Mo-POMs, W-POMs possess higher structural stability and show stronger binding and oxidation effect on PrP. Additionally, the substitution of W/Mo by vanadium elevates the local electron distribution on the bridged O(26) atom, thereby strengthening the hydrogen bonding of POMs with the histidine site. Most importantly, with the number of substituted vanadium increases, the LUMO energy level of POMs decreases, making it easier to accept electrons from methionine. As a result, PW10V2 displays the strongest oxidation on the methionine residue of PrP, leading to an excellent inhibitory effect on PrP aggregation and a significant attenuation on its neurotoxicity.