Assembly of Titanium‐oxo Clusters from Embonic Acid‐Modified {Ti₂} Molecular Building Blocks with Efficient Sulfur‐Catalyzed Oxidation Activities

To design and synthesize high‐nucleated titanium‐oxo clusters rationally based on molecular building blocks with potential coordination ability is still a great challenge. In this work, a family of titanium‐oxo clusters, including Ti 2 , Ti 6 , Ti 12 , and Ti 20 clusters, have been assembled from large‐size ligand embonic acid‐modified {Ti 2 } molecular building blocks under solvothermal conditions. By modulating auxiliary linkers and solvent types, the {Ti 2 } building blocks exhibit varying degrees of polymerization to form high‐nuclear titanium‐oxo clusters. Notably, Ti 20 with high nucleation, as the decamer containing {Ti 2 } building blocks, can act as a stable and heterogeneous catalyst to efficiently catalyze the oxidation of sulfides to sulfones and sulfoxides when using H 2 O 2 as the green oxidant. This study provides a new approach for the design and synthesis of highly nucleated and homometallic TOCs based on {Ti 2 } units.