Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr6 clusters

• Published in: Chemical science (Cambridge) Vol. 15; no. 9; pp. 3174 - 3181
• Main Authors: Peng, Tianyou, Chao-Qin, Han, Hai-Lun Xia, Zhou, Kang, Zhang, Jian, Si, Jincheng, Wang, Lei, Miao, Jiafeng, Fu-An, Guo, Wang, Hao, Lu-Lu, Qu, Xu, Guozhong, Li, Jing, Xiao-Yuan, Liu
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 28.02.2024; The Royal Society of Chemistry
• Subjects: Aqueous solutions; Carboxylic acids; Chemistry; Clusters; Hydroxyl groups; Metal-organic frameworks; Structural analysis; Thermal stability; Topology; Zirconium
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d3sc05410a

Zirconium-based metal–organic frameworks (Zr-MOFs) have been extensively studied due to their very rich structural chemistry. The combination of nearly unlimited carboxylic acid-based linkers and Zr6 clusters with multiple connectivities has led to diverse structures and specific properties of resultant Zr-MOFs. Herein, we demonstrate the successful use of reticular chemistry to construct two novel Zr-MOFs, HIAM-4040 and HIAM-4040-OH, with zfu topology. Based on a thorough structural analysis of (4,4)-connected lvt-type Zr-tetracarboxylate frameworks and a judicious linker design, we have obtained the first example of a Zr-pentacarboxylate framework featuring unprecedented 5-connected organic linkers and 5-connected Zr6 clusters. Compared with HIAM-4040, a larger Stokes shift is achieved in HIAM-4040-OH via hydroxyl group induced excited-state intramolecular proton transfer (ESIPT). HIAM-4040-OH exhibits high chemical and thermal stability and is used for HClO detection in aqueous solution with excellent sensitivity and selectivity.