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

Abstract

AbstractPentagonal {Ti(Ti5)} 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)2NH2]2[Ti21O29(OiPr)12(DMF)6(SO4)8] ({Ti21}) based on {Ti(Ti5)} motifs had been obtained under hydrothermal conditions. It possesses ‘fused’ dimeric {Ti11} as well as trimeric {Ti12} subunits featuring unexpected bonding modes based on pentagonal {Ti(Ti5)} motifs. Furthermore, {Ti21} exhibits good water and solvent tolerance. As an atomically precise TOCs‐based semiconductor photocatalyst, {Ti21} exhibits appreciable photocatalytic hydrogen evolution activity with an optimal hydrogen generation rate of 191.94 μmol/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.