Synthesis, Structure and Light-Driven H2 Production of a {Ti21} Titanium-Oxo Cluster Featuring Pentagonal {Ti(Ti5)} Motifs

Pentagonal {Ti(Ti-5)} motifs play a crucial role during the assembly of novel titanium-oxide clusters (TOCs), whose development is still in its infancy. In this work, an unprecedented TOC [(CH3)(2)NH2](2)[Ti21O29(OiPr)(12)(DMF)(6)(SO4)(8)] ({Ti-21}) based on {Ti(Ti-5)} motifs had been obtained under hydrothermal conditions. It possesses 'fused' dimeric {Ti-11} as well as trimeric {Ti-12} subunits featuring unexpected bonding modes based on pentagonal {Ti(Ti-5)} motifs. Furthermore, {Ti-21} exhibits good water and solvent tolerance. As an atomically precise TOCs-based semiconductor photocatalyst, {Ti-21} exhibits appreciable photocatalytic hydrogen evolution activity with an optimal hydrogen generation rate of 191.94 mu mol/g/h under UV/Vis light. This work provides significant advances and favorable models for the further synthesis of TOCs with unique structure and functionality.

Automated summary

In this work, a novel titanium-oxide cluster {Ti-21} based on pentagonal {Ti(Ti-5)} motifs was synthesized under hydrothermal conditions. It exhibits 'fused' dimeric {Ti-11} and trimeric {Ti-12} subunits with unexpected bonding modes. Additionally, {Ti-21} shows good water and solvent tolerance and demonstrates appreciable photocatalytic hydrogen evolution activity.