Issue 29, 2024

Synthesis of polyoxothiometalates through site-selective post-editing sulfurization of polyoxometalates

Abstract

Polyoxometalates (POMs) function as platforms for synthesizing structurally well-defined inorganic molecules with diverse structures, metals, compositions, and arrangements. Although post-editing of the oxygen sites of POMs has great potential for development of unprecedented structures, electronic states, properties, and applications, facile methods for site-selective substitution of the oxygen sites with other atoms remain limited. Herein, we report a direct site-selective oxygen–sulfur substitution method that enables transforming POMs [XW12O40]4− (X = Si, Ge) to Keggin-type polyoxothiometalates (POTMs) [XW12O28S12]4− using sulfurizing reagents in an organic solvent. The resulting POTMs retain the original Keggin-type structure, with all 12 surface W[double bond, length as m-dash]O groups selectively converted to W[double bond, length as m-dash]S without sulfurization of other oxygen sites. These POTMs show high stability against water and O2 in organic solvents and a drastic change in the electronic states and redox properties. The findings of this study represent a facile method for converting POMs to POTMs, leading to the development of their unique properties and applications in diverse fields, including (photo)catalysis, sensing, optics, electronics, energy conversion, and batteries.

Graphical abstract: Synthesis of polyoxothiometalates through site-selective post-editing sulfurization of polyoxometalates

Supplementary files

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Article information

Article type
Edge Article
Submitted
02 May 2024
Accepted
11 Jun 2024
First published
14 Jun 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 11267-11271

Synthesis of polyoxothiometalates through site-selective post-editing sulfurization of polyoxometalates

K. Yonesato, K. Yamaguchi and K. Suzuki, Chem. Sci., 2024, 15, 11267 DOI: 10.1039/D4SC02912G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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