Breaking the Gordian Knot in the Structural Chemistry of Polyoxometalates: Copper(II)–Oxo/Hydroxo Clusters

This Concept article provides insights into the molecular design and construction aspects of polyoxocuprates (POCus), an emerging class of polyoxometalate (POM)-like architectures featuring low-to-high nuclearity copper(II)-oxo/hydroxo skeletons. POCus have been identified to adopt the structural principles of classical POMs consisting of early transition metals. Their potential to afford motifs of the noble-metal-based POMs is exploited. "Cross-structural topological transformation" is introduced to generalize skeletal relationships between POCus and POMs. The study opens up strategies toward the brand-new structural chemistry of POCus with relevance to homogeneous photocatalysis, medicinal chemistry, molecular magnetism, and quantum computing.