Ju Yu, Li Zi-Jian, Lu Huangjie, Zhou Zhengyang, Li Yongxin, Wu Xiao-Ling, Guo Xiaofeng, Qian Yuan, Zhang Zhi-Hui, Lin Jian, Wang Jian-Qiang, He Ming-Yang
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University, Changzhou, Jiangsu Province 213164, P. R. China.
Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, P. R. China.
Inorg Chem. 2021 Apr 19;60(8):5617-5626. doi: 10.1021/acs.inorgchem.0c03586. Epub 2021 Mar 19.
The rational design and synthesis of metal-organic frameworks with well-controlled interpenetration have been active research areas of inquiry, particularly for porosity-related applications. Herein, we extend the use of the ligand steric modulation strategy to initiate the first study of the interpenetration control of thorium-based MOFs. The approximate "hardness" of the Th cation, which was conjugated with aromatic substitutions and delicately modified synthetic conditions, allows for the crystallization of single crystals of seven new Th-MOFs with five distinct topologies. Solvothermal reactions of Th(NO) with the triphenyl HTPDC ligand under variable conditions exclusively gave rise to an interpenetrated Th-MOF with a topology, namely . Modifications of the ligand sterics with two pendant methyl groups to 2',5'-MeTPDC and 2,2″-MeTPDC afforded two noninterpenetrated UiO-68-type Th-MOFs ( and , respectively) with record-high pore volumes (74.8% and 75.3%, respectively) among all the thorium MOFs. Moreover, another four Th-MOFs ( = 18, 19, 21, and 22) with three different topologies were obtained by a simple synthetic modulation. Notably, and represent the second rare examples of interpenetrated Th-MOFs reported to date. These findings revealed the unprecedented structural complexity and synthetic accessibility of Th-MOFs among all tetravalent metal containing MOFs. Such features make Th-MOFs as an ideal platform to elucidate the structure-property relationship for various applications, e.g. iodine adsorption.
合理设计与合成具有可控互穿结构的金属有机框架一直是活跃的研究领域，特别是在与孔隙率相关的应用方面。在此，我们扩展了配体空间调制策略的应用，首次开展了基于钍的金属有机框架互穿控制的研究。与芳香取代基共轭并精细调节合成条件的钍阳离子的近似“硬度”，使得能够结晶出七种具有五种不同拓扑结构的新型钍基金属有机框架单晶。在可变条件下，硝酸钍与三苯基 HTPDC 配体的溶剂热反应仅生成了一种具有 拓扑结构的互穿钍基金属有机框架，即 。用两个侧链甲基对配体空间进行修饰得到 2',5'-MeTPDC 和 2,2″-MeTPDC，得到了两种非互穿的 UiO-68 型钍基金属有机框架（分别为 和 ），在所有钍基金属有机框架中具有创纪录的高孔体积（分别为 74.8%和 75.3%）。此外，通过简单的合成调节获得了另外四种具有三种不同拓扑结构的钍基金属有机框架 （ = 18、19、21 和 22）。值得注意的是， 和 是迄今为止报道的互穿钍基金属有机框架的第二个罕见例子。这些发现揭示了钍基金属有机框架在所有含四价金属的金属有机框架中前所未有的结构复杂性和合成可及性。这些特性使钍基金属有机框架成为阐明各种应用（如碘吸附）结构-性能关系的理想平台。
