Synthesis of a Keggin-type polyoxoselenidotungstate via site-selective oxygen-to-selenium substitution

Abstract

Selenium, a group 16 (chalcogen) element, can endow metal oxides with unique properties when replacing oxygen atoms from specific sites. Polyoxometalates (POMs), a class of anionic metal oxide clusters, exhibit structure-dependent properties and applications. Despite the potential of chalcogen substitution, the replacement of oxygen atoms in POMs with chalcogens has been rarely explored. In a recent study, we demonstrated site-selective oxygen-to-sulfur substitution in the Keggin-type POM [SiW12O40]4−. Building on this, we now report the first synthesis of a polyoxoselenidotungstate, featuring terminal selenido ligands (W[double bond, length as m-dash]Se bonds), using a site-selective oxygen-to-selenium substitution reaction. By reacting [SiW12O40]4− with Woollins' reagent (2,4-diphenyl-1,3,2,4-diselenadiphosphetane 2,4-diselenide) in organic solvents, all twelve terminal oxido ligands (W[double bond, length as m-dash]O) were selectively converted to selenido ligands (W[double bond, length as m-dash]Se). The resulting compound [SiW12O28Se12]4− retains the Keggin-type framework and exhibits distinct optical and electronic properties owing to the incorporated selenium atoms. These findings pave the way for the systematic modification of oxygen sites in POMs with the heavier chalcogens sulfur and selenium, opening new avenues for tailoring their properties and expanding their utility across diverse fields of materials science.

Graphical abstract: Synthesis of a Keggin-type polyoxoselenidotungstate via site-selective oxygen-to-selenium substitution

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Article information

Article type
Edge Article
Submitted
08 May 2025
Accepted
15 Jun 2025
First published
16 Jun 2025
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., 2025, Advance Article

Synthesis of a Keggin-type polyoxoselenidotungstate via site-selective oxygen-to-selenium substitution

K. Yonesato, Y. Watanabe, M. Pascual-Borràs, R. J. Errington, K. Yamaguchi and K. Suzuki, Chem. Sci., 2025, Advance Article , DOI: 10.1039/D5SC03340C

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