The transformation of polyoxometalates in the formation of intercluster compound [Ag41(α-SiW(10)O37)((t)BuC≡C)27(CH3CN)3][β-SiW(12)O40].

We report a unique intercluster compound comprising a Ag41 cage encapsulating a divacant [α-SiW(10)O37](10-) anion and a complete [β-SiW(12)O40](4-) anion as a counteranion. Two electro-redox centers associated with the inner and outer POM anions show interesting electrochemical behaviours, because the stable Ag41 cage acts as an electron transfer mediator.

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