Synthesis Strategies and Structures of Molecular Heterometallic Oxo Clusters

Multinuclear heterometallic oxo clusters, composed of two or more different metal cations bridged by oxo ligands, represent an important class of molecular complexes known for their unique magnetic, catalytic, and electrochemical properties resulting from cooperative interactions between the metal cations. If three or more types of metal cations can be arranged as designed, their chemical and physical properties can be precisely and flexibly controlled, potentially creating innovative materials. However, research on hetero-trimetallic and hetero-tetrametallic oxo clusters remains limited. This review presents an interdisciplinary search of multinuclear heterometallic oxo clusters, regardless of the type of ligand, to explain and classify their synthesis strategies and structures. By cataloging crystallographically characterized heterometallic oxo clusters using ligand-per-metal values and synthesis method notations, valuable insights have been gained into effective synthesis methods for the precise arrangement of metal cations. The advantages and disadvantages of one-pot synthesis methods and synthesis strategies for achieving precise structural control of heterometallic oxo clusters are discussed with an emphasis on the prediction of their final structures. The insights from this review are expected to drive the development of synthetic and analytical techniques for the precise synthesis of heterometallic complexes in a predictable way.