水杨醛肟和乙酰氧肟酸钛氧簇合物的合成及光电性质

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

通过溶剂热合成方法,以水杨醛肟(H_(2)Saox)和乙酰氧肟酸(H_(2)Ahox)为染料敏化功能配体,分别以异丁酸(HiBuac)和苯基膦酸(PhPO_(3)H_(2))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[Ti_(6)(μ_(3)-O)_(4)(Saox)_(2)(iBuac)_(4)(OiPr)_(8)](1)和八核钛氧簇配合物[Ti_(8)(μ_(3)-O)_(2)(Ahox)_(2)(PhPO_(3))_(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(H_(2)Saox),isobutyric acid(HiBuac),and Ti(OiPr)_(4)the hexanuclear titanium oxo cluster(TOC)of[Ti_(6)(μ_(3)-O)_(4)(Saox)_(2)(iBuac)_(4)(OiPr)_(8)](1)was solvothermally synthesized,and by the reaction of acetohydroxamic acid(H_(2)Ahox),phenylphosphonic acid(PhPO_(3)H_(2))and Ti(OiPr)_(4)the octa-nuclear TOC of[Ti_(8)(μ_(3)-O)_(2)(Ahox)_(2)(PhPO_(3))_(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 H_(2)Ahoxbased TOCs that showed photocatalytic H_(2)evolution activity with the rate of 140.2μmol·g^(-1)·h^(-1).CCDC:225_(16)56,1;225_(16)57,2.