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Updated: Jul 1, 2025
Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr6
Tianyou Peng1,2, Chao-Qin Han1, Hai-Lun Xia1
1Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic University 7098 Liuxian Blvd, Nanshan District Shenzhen 518055 P. R. China liuxiaoyuan1989@szpu.edu.cn jingli@rutgers.edu.
Abstract:
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.
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