Syntheses and photoelectric properties of titanium oxo clusters assembled by salicylaldoxime and acetohydroxamic acid

In this work, by the reaction of salicylaldoxime (H(2)Saox), isobutyric acid (H(i)Buac), and Ti((OPr)-Pr-i)(4) the hexanuclear titanium oxo cluster (TOC) of [Ti-6(mu(3)-O)(4)(Saox)(2)((i)Buac)(4)((OPr)-Pr-i)(8)] (1) was solvothermally synthesized, and by the reaction of acetohydroxamic acid (H(2)Ahox), phenylphosphonic acid (PhPO3H2) and Ti((OPr)-Pr-i)(4) the octa-nuclear TOC of [Ti-8(mu(3)-O)(2)(Ahox)(2)(PhPO3)(4)((OPr)-Pr-i)(16)] (2) was prepared. Both of them were characterized by IR, elemental analyses, and single-crystal X-ray diffraction. Spectral experiments indicate that the two complexes have absorptions in the visible region. The band gaps of complexes 1 and 2 were 2.43 and 2.61 eV respectively. Complex 2 is the first H(2)Ahox-based TOCs that showed photocatalytic H-2 evolution activity with the rate of 140.2 mu mol center dot g(-1)center dot h(-1). CCDC: 2251656, 1; 2251657, 2.