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Polyoxometalate {W18O56XO6} clusters with embedded redox-active main-group templates as localized inner-cluster radicals.

Non-mixed-valent reduced polyoxometalates, namely {W18O56XO6} Dawson-like clusters (X=IVII or TeVI) with a localized redox active template have been synthesized and redox properties compared with the pure tungsten control (that is, X=WVI). Upon one-electron reduction, the electron localizes on the main-group element, giving IVI or TeV, respectively. These clusters have potential as a new type of electron-transfer reagent.