Application of Hard and Soft Acid‐base Theory to Construct Heterometallic Materials with Metal‐oxo Clusters

Abstract Heterometallic cluster‐based materials offer the potential to incorporate multiple functionalities, leveraging the aggregation effects of clusters and translating this heterogeneity and complexity into unexpected properties that are more than just the sum of their components. However, the rational construction of heterometallic cluster‐based materials remains challenging due to the complexity of metal cation coordination and structural unpredictability. This minireview provides insights into a general synthetic strategy based on Hard and Soft Acids and Bases (HSAB) theory, summarizing its advantages in the designed synthesis of discrete heterometallic clusters (intracluster assembly) and infinite heterometallic cluster‐based materials (intercluster assembly). Furthermore, it emphasizes the potential to exploit the intrinsic properties of mixed components to achieve breakthroughs across a broad range of applications. The insights from this review are expected to drive the progress of heterometallic cluster‐based materials in a controllable and predictable manner.