Liu Xiao-Xue, Chen Guang-Hui, Tao Jun, Zhang Jian, Zhang Lei
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Liangxiang Campus, Beijing Institute of Technology, Beijing 102488, People's Republic of China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China.
Inorg Chem. 2022 Jan 24;61(3):1385-1390. doi: 10.1021/acs.inorgchem.1c02891. Epub 2022 Jan 11.
Exploring new structural types of polyoxotitanium clusters (PTCs), especially those containing classical polyoxometalates structures, has always been the focus of research in the field of metal-oxo clusters. In this work, we present the synthesis and characterization of three prismatic PTCs: namely, Ti(μ-O)(μ-O)(OPr)(HOPr)(L1) (; HL1 = 3,5-di--butylcatechol), Ti(μ-O)(μ-O)(OPr)(L2)(L3) (; HL2 = 1-adamantanecarboxylic acid, HL3 = 2-picolinic acid), and Ti(μ-O)(μ-O)(μ-O)(OPr)(L3) (). Single-crystal X-ray diffraction analyses indicate that the construction of these prismatic PTCs is based on a stepwise interlayer assembly of {Ti} and {Ti} substructures. The diameters of their core skeletons are in the range between 0.9 and 1.3 nm. In particular, lacunary Linqvist-like {Ti} and {Ti} building units are found to exist in the structures of and . According to the solid-state UV-vis diffuse reflectance measurements, the absorption band of 3,5-di--butylcatecholate-functionalized shifts toward the visible-light region, giving a smaller optical band gap of 1.56 eV in comparison to (3.36 eV) and (3.25 eV).
探索新型多氧钛簇（PTCs）的结构类型，尤其是那些包含经典多金属氧酸盐结构的类型，一直是金属氧簇领域的研究重点。在这项工作中，我们报道了三种棱柱形PTCs的合成与表征：即Ti(μ-O)(μ-O)(OPr)(HOPr)(L1)（；HL1 = 3,5-二叔丁基邻苯二酚）、Ti(μ-O)(μ-O)(OPr)(L2)(L3)（；HL2 = 1-金刚烷甲酸，HL3 = 2-吡啶甲酸）和Ti(μ-O)(μ-O)(μ-O)(OPr)(L3)（）。单晶X射线衍射分析表明，这些棱柱形PTCs的构建基于{Ti}和{Ti}子结构的逐步层间组装。它们核心骨架的直径在0.9至1.3纳米之间。特别地，在 和 的结构中发现存在类Lindqvist型的缺位{Ti}和{Ti}构筑单元。根据固态紫外-可见漫反射测量，3,5-二叔丁基邻苯二酚官能化的 的吸收带向可见光区域移动，与 （3.36 eV）和 （3.25 eV）相比，其光学带隙更小，为1.56 eV。
