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The introduction of coinage metals (CMs) into lacunary polyoxometalates (POMs) to construct CM-substituted POMs (CM-POMs) has attracted increasing interest over the past decade. This is because CM-POMs combine the unique structural features of POMs and CMs and have promising applications in photocatalysis, luminescence, magnetic materials, etc. In this review, the structural characteristics, synthesis methods, and applications of CM-POMs are summarized in three categories according to the type of their metal core element: Cu-, Ag-, and Au-substituted POMs. Furthermore, this paper discusses the current challenges regarding investigations into the design and properties of CM-POMs.
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