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Lookup NU author(s): Dr Magda Pascual-BorrasORCiD, Dr John ErringtonORCiD
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Selenium, a group 16 (chalcogen) element, can endow metal oxides with unique properties when replacingoxygen atoms from speci c sites. Polyoxometalates (POMs), a class of anionic metal oxide clusters, exhibitstructure-dependent properties and applications. Despite the potential of chalcogen substitution, thereplacement of oxygen atoms in POMs with chalcogens has been rarely explored. In a recent study, wedemonstrated site-selective oxygen-to-sulfur substitution in the Keggin-type POM [SiW12O40]4−. Buildingon this, we now report the rst synthesis of a polyoxoselenidotungstate, featuring terminal selenidoligands (W]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) inorganic solvents, all twelve terminal oxido ligands (W]O) were selectively converted to selenido ligands(W]Se). The resulting compound [SiW12O28Se12]4− retains the Keggin-type framework and exhibitsdistinct optical and electronic properties owing to the incorporated selenium atoms. These ndings pavethe way for the systematic modi cation of oxygen sites in POMs with the heavier chalcogens sulfur andselenium, opening new avenues for tailoring their properties and expanding their utility across diverseelds of materials science.
Author(s): Yonesato K, Watanabe Y, Pascual-Borras M, Errington RJ, Yamaguchi K, Suzuki K
Publication type: Article
Publication status: Published
Journal: Chemical Science
Year: 2025
Volume: 16
Issue: 29
Pages: 13183-13188
Online publication date: 16/06/2025
Acceptance date: 15/06/2025
Date deposited: 14/07/2025
ISSN (print): 2041-6520
ISSN (electronic): 2041-6539
Publisher: Royal Society of Chemistry
URL: https://doi.org/10.1039/d5sc03340c
DOI: 10.1039/d5sc03340c
Data Access Statement: The data supporting this manuscript are available in the ESI and available on request. Crystallographic data for TPP salts of [SiW12O40]4- and [SiW12O28Se12]4- have been deposited at the CCDC (deposition numbers 2440303 and 2440307).
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