Electron Delocalization and Transfer Across Polyoxometalates‐Based Subnanomaterials in Catalytic Reactions

Abstract Due to their identical building blocks and high surface‐to‐volume ratio, subnanomaterials exhibit significant properties compared to their bulk nanomaterial counterparts. The interactions between these building blocks can result in either equal or unequal sharing of electrons, leading to electron transfer in heterojunctions or electron delocalization within symmetric structures. Clusters, possessing electronic properties akin to atoms, can serve as reservoirs of electrons to stabilize crucial intermediates in catalytic reactions. This perspective provides a novel understanding of well‐defined subnanomaterials with distinct architectures, such as cluster‐based constructions and co‐assembled heterojunctions, emphasizing the relationship between electronic structures and catalytic properties. The objective is to provide novel perspectives on the realm of subnanomaterials and cluster‐based architectures.