State Key Laboratory of Structural Chemistry , Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou , Fujian 350002 , China.
University of Chinese Academy of Sciences , 100049 Beijing , China.
Inorg Chem. 2018 Aug 6;57(15):8850-8856. doi: 10.1021/acs.inorgchem.8b00751. Epub 2018 Jul 23.
Six crystalline polyoxo-titanium clusters (PTCs) derived from oximes, namely, Ti(μ-O)(OMe)(L1) (PTC-125; HL1 = salicylaldoxime), H[Ti(μ-O)(μ-O)(OMe)(L1)] (PTC-126), Ti(μ-O)(μ-O)(O Pr)(OAc)(L2) (PTC-127; HL2 = salicylhydroxamic acid; HOAc = acetic acid), Ti(μ-O)(OEt)(L2) (PTC-128), Ti(μ-O)(μ-O)(OEt)(L2) (PTC-129), and Ti(μ-O)(μ-O)(μ-O)(OEt)(L3) (PTC-130; HL3 = acetoxime) have been solvothermally synthesized and structurally characterized. Compared with the reported solid-state monomer, dimer, trimer, and tetramer titanium oximes, these compounds possess high nuclearity structures in the range Ti, Ti, Ti, Ti, Ti, and Ti as a result of the presence of oxo bridges. Even though three examples of tetranuclear and hexanuclear derivatives have been documented, PTC-130 with a centrosymmetric Ti cluster core represents the currently highest PTC compound in the oxime system. In addition, Ti/oximate ratio by solvothermal synthesis in this work possessed a broad range from 0.83:1 to 9:1, different from the constant ratio of 1:1 in the reported ones. According to the solid-state UV-vis diffuse reflectance measurement, the existence of oxime ligands largely enhanced their visible light harvest. Furthermore, their photocurrent response properties are also studied.
六种源自肟的晶态多氧钛簇（PTC），即 Ti(μ-O)(OMe)(L1)（PTC-125；HL1 = 水杨醛肟）、H[Ti(μ-O)(μ-O)(OMe)(L1)]（PTC-126）、Ti(μ-O)(μ-O)(O Pr)(OAc)(L2)（PTC-127；HL2 = 水杨羟肟酸；HOAc = 乙酸）、Ti(μ-O)(OEt)(L2)（PTC-128）、Ti(μ-O)(μ-O)(OEt)(L2)（PTC-129）和 Ti(μ-O)(μ-O)(μ-O)(OEt)(L3)（PTC-130；HL3 = 乙肟），通过溶剂热合成法被合成并进行了结构表征。与已报道的固态单体、二聚体、三聚体和四聚体钛肟相比，由于存在氧桥，这些化合物具有高核钛氧簇结构，范围为 Ti、Ti、Ti、Ti、Ti 和 Ti。尽管已经有三个四核和六核衍生物的例子，但 PTC-130 具有中心对称的 Ti 簇核，代表了肟体系中目前最高的 PTC 化合物。此外，与已报道的固定比例 1:1 不同，本工作中通过溶剂热合成得到的 Ti/肟比具有较宽的范围，从 0.83:1 到 9:1。根据固态紫外-可见漫反射测量，肟配体的存在大大增强了它们对可见光的吸收。此外，还研究了它们的光电流响应特性。
