Exploration of Controllable Synthesis and Structural Diversity of Titanium─Oxo Clusters

Titanium-oxo clusters (TOCs), form a significant branch of metal-oxo cluster chemistry, often featuring atomically well-defined structures. A small number of TOCs are anionic in nature and capped with inorganic ligands or other components. Most recently, coordination delayed hydrolysis (CDH) strategies have paved the way to fabricating novel TOCs by controlling the degree of Ti 4+ hydrolysis to facilitate their crystallization. This chapter provides a discussion of CDH strategies to prepare TOCs, followed by an analysis on recent progress concerning cluster core diversity, highlighting some of the most compelling cases of TOCs to illustrate different cluster core types. It outlines the ligand diversity and its advantages in synthetic control. The chapter illustrates the diversity of metal-doping strategies, including transition metal doping and rare earth metal doping. It then describes the bandgap engineering of TOCs and potential applications in photo-related fields.