Confinement Effects of Coordination Cages on the Synthesis and Application of Polyoxometalates

The confinement effects within coordination cages present powerful tools in modern chemistry, particularly for the synthesis and manipulation of complex molecules. This concept article reviews the use of coordination cages to stabilize and tune the properties of polyoxometalates (POMs), a class of nano‐sized metallic clusters, expanding the focus beyond traditional organic reactions. The article provides a brief overview of coordination cages, and POM chemistry and discusses the encapsulation of POMs in coordination cages, highlighting how these cages provide a confinement effect that enhances the stability and reactivity of POMs. Additionally, the concept of cavity‐directed synthesis is explored as a method for creating labile POMs, which are often unstable in aqueous conditions, underlining its implications for supramolecular catalysis. Future research will focus on expanding the structures and applications of encapsulated POMs, as well as improving cage designs to unlock new cluster architectures.