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

We report the synthesis, structure and photocatalytic H₂ production of a rare example of {Ti(Ti₅)}-containing titanium-oxide cluster, namely [(CH₃)₂NH₂]₂[Ti₂₁O₂₉(OiPr)₁₂(DMF)₆(SO₄)₈], which possesses ‘fused’ dimeric {Ti₁₁} as well as trimeric {Ti₁₂} subunits featuring unprecedented bonding modes based on pentagonal {Ti(Ti₅)} motifs.

Abstract

Pentagonal {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.

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