Huang Guo-Quan, Chen Jun, Huang Yong-Liang, Wu Kun, Luo Dong, Jin Ji-Kang, Zheng Ji, Xu Shi-Hai, Lu Weigang
College of Chemistry and Materials Science, Jinan University, Guangzhou 510632, P. R. China.
Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications, Jinan University, Guangzhou 510632, P. R. China.
Inorg Chem. 2022 May 30;61(21):8339-8348. doi: 10.1021/acs.inorgchem.2c00941. Epub 2022 May 14.
Multicomponent metal-organic frameworks (MOFs) have received an increasing amount of attention due to their potential to produce new topologies, pore metrics, and functionalities compared to MOFs with a single metal cluster and one organic linker. Herein, five isoreticular Zn MOFs were obtained by mixing two types of linear ditopic linkers in a one-pot solvothermal synthesis. Interestingly, in the resulting Zn MOFs a six-connected cyclic trinuclear Zn(II) cluster and an eight-connected linear trinuclear Zn(II) cluster coexist, leading to an uncommon (6,8)-connected network. Catalytic activities toward the solvent-free Knoevenagel reactions were observed for all of these MOFs. Further experimental and computational studies suggest that they are Brønsted acid-base bifunctional catalysts. Through chemical modifications of dicarboxylate ligands, including their aromatic backbones and substituents, we have successfully implemented reticular chemistry for the modulations of pore sizes, surface areas, and catalytic performances in a series of four-component isoreticular MOFs.
与具有单一金属簇和一种有机连接体的金属有机框架（MOF）相比，多组分金属有机框架因其具有产生新拓扑结构、孔尺寸和功能的潜力而受到越来越多的关注。在此，通过在一锅溶剂热合成中混合两种类型的线性双齿连接体，获得了五种同构的锌基金属有机框架。有趣的是，在所得的锌基金属有机框架中，一个六连接的环状三核锌（II）簇和一个八连接的线性三核锌（II）簇共存，形成了一种罕见的（6,8）连接网络。观察到所有这些金属有机框架对无溶剂Knoevenagel反应均具有催化活性。进一步的实验和计算研究表明，它们是布朗斯特酸碱双功能催化剂。通过对二羧酸配体进行化学修饰，包括其芳环骨架和取代基，我们成功地在一系列四组分同构金属有机框架中实施了网状化学，以调节孔径、表面积和催化性能。
