通过溶剂热合成方法,以水杨醛肟(H2Saox)和乙酰氧肟酸(H2Ahox)为染料敏化功能配体,分别以异丁酸(HiBuac)和苯基膦酸(PhPO3H2)为辅助配体,与钛酸四异丙酯(Ti(OiPr)4)反应,合成了六核钛氧簇配合物[Ti6(μ3-O)4(Saox)2(iBuac)4(OiPr)8](1)和八核钛氧簇配合物[Ti8(μ3-O)2(Ahox)2(PhPO3)4(OiPr)16](2).配合物1和2均通过红外光谱、元素分析和单晶X射线衍射进行了结构表征.光谱性质表明,配合物1和2在可见光区均有吸收,其带隙分别为2.43和2.61 eV.配合物2是首个基于乙酰氧肟酸的钛氧簇,具有光催化析氢性能且速率可达140.2μmol·g-1·h-1.
In this work,by the reaction of salicylaldoxime(H2Saox),isobutyric acid(HiBuac),and Ti(OiPr)4 the hexa-nuclear titanium oxo cluster(TOC)of[Ti6(μ3-O)4(Saox)2(iBuac)4(OiPr)8](1)was solvothermally synthesized,and by the reaction of acetohydroxamic acid(H2Ahox),phenylphosphonic acid(PhPO3H2)and Ti(OiPr)4 the octa-nuclear TOC of[Ti8(μ3-O)2(Ahox)2(PhPO3)4(OiPr)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 H2Ahox-based TOCs that showed photocatalytic H2 evolution activity with the rate of 140.2 μmol·g-1·h-1.CCDC:2251656,1;2251657,2.