Reticular Chemistry Directed “One‐Pot” Strategy to in situ Construct Organic Linkers and Zirconium‐Organic Frameworks

• Published in: Small (Weinheim an der Bergstrasse, Germany) Vol. 20; no. 36; pp. e2402263 - n/a
• Main Authors: Han, Chao‐Qin, Wang, Lei, Si, Jincheng, Zhou, Kang, Liu, Xiao‐Yuan
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.09.2024
• Subjects: Aldehydes; benzimidazole; Carboxylic acids; Chemical synthesis; Metal-organic frameworks; multitopic carboxylic acids; one‐pot strategy; Phenylenediamine; reticular chemistry; Zirconium; benzimidazole; metal–organic frameworks; reticular chemistry; multitopic carboxylic acids; one‐pot strategy
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202402263

Zirconium‐based metal–organic frameworks (Zr‐MOFs) have emerged as one of the most studied MOFs due to the unlimited numbers of organic linkers and the varying Zr‐oxo clusters. However, the synthesis of carboxylic acids, especially multitopic carboxylic acids, is always a great challenge for the discovery of new Zr‐MOFs. As an alternative approach, the in situ “one‐pot” strategy can address this limitation, where the generation of organic linkers from the corresponding precursors and the sequential construction of MOFs are integrated into one solvothermal condition. Herein, inspired by benzimidazole‐contained compounds synthesized via reaction of aldehyde and o‐phenylenediamine, tri‐, tetra‐, penta‐ and hexa‐topic carboxylic acids and a series of corresponding Zr‐MOFs can be prepared via the in situ “one‐pot” method under the same solvothermal conditions. This strategy can be utilized not only to prepare reported Zr‐MOFs constructed using benzimidazole‐contained linkers, but also to rationally design, construct and realize functionalities of zirconium‐pentacarboxylate frameworks guided by reticular chemistry. More importantly, in situ “one‐pot” method can facilitate the discovery of new Zr‐MOFs, such as zirconium‐hexacarboxylate frameworks. The present study demonstrates the promising potential of benzimidazole‐inspired in situ “one‐pot” approach in the crystal engineering of structure‐ and property‐specific Zr‐MOFs, especially with the guidance of reticular chemistry. Inspired by reaction between aldehyde and o‐phenylenediamine, tri‐, tetra‐, penta‐ and hexa‐topic carboxylic acids are synthesized, which are used to construct zirconium‐based metal‐organic frameworks (Zr‐MOFs) via the in situ “one‐pot” strategy. This strategy can be utilized not only to prepare reported Zr‐MOFs, but also to rationally design, construct and realize the functionalities of zirconium‐pentacarboxylate frameworks guided by reticular chemistry.