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

A family of titanium-oxo clusters were assembled from large-size ligand embonic acid-modified {Ti₂} molecular building blocks under solvothermal conditions and Ti₂₀ with a large nuclear number has been used as a stable and heterogeneous catalyst to catalyze sulfur oxidation reactions efficiently.

Abstract

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 Ti₂ , Ti₆ , Ti₁₂ , and Ti₂₀ clusters, have been assembled from large-size ligand embonic acid-modified {Ti₂} molecular building blocks under solvothermal conditions. By modulating auxiliary linkers and solvent types, the {Ti₂} building blocks exhibit varying degrees of polymerization to form high-nuclear titanium-oxo clusters. Notably, Ti₂₀ with high nucleation, as the decamer containing {Ti₂} building blocks, can act as a stable and heterogeneous catalyst to efficiently catalyze the oxidation of sulfides to sulfones and sulfoxides when using H₂O₂ as the green oxidant. This study provides a new approach for the design and synthesis of highly nucleated and homometallic TOCs based on {Ti₂} units.

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