Zirconium‐Pentacarboxylate Frameworks with Coexisted 4‐ and 9‐Connected Zr6 Clusters for Detection and Removal of Tetracycline Hydrochloride

• Published in: Advanced optical materials 2024-06, Vol.12 (17), p.n/a
• Main Authors: Peng, Tianyou, Han, Chao‐Qin, Zhou, Kang, Wang, Lei, Xu, Guozhong, Liu, Xiao‐Yuan
• Format: Article
• Language: English
• Subjects: Carboxylic acids; Clusters; coexisted Zr6 clusters; detection; Metal-organic frameworks; novel topology; tunable emission; Zirconium; zirconium‐pentacarboxylate frameworks
• ISSN: 2195-1071; 2195-1071
• DOI: 10.1002/adom.202303277

Due to the varying connectivity of Zr6 cluster and unlimited carboxylic acid‐based organic linkers, zirconium‐based metal‐organic frameworks (Zr‐MOFs) exhibit the most abundant structural diversity. However, Zr‐MOFs possessing more than one kind of Zr6 clusters in a single structure have not yet been reported. Herein, four new pentacarboxylic acids are synthesized to prepare Zr‐MOFs, HIAM‐4051 to HIAM‐4054. As a result, due to the different lengths of linkers, two novel underlying nets (typ and cqh) are found in these four MOFs with coexisting 4‐ and 9‐connected Zr6 clusters. Furthermore, by changing the acceptor groups in the linker skeleton, the emission of results Zr‐MOFs can be customized from blue, yellow–green to red. The nano‐sized HIAM‐4053‐NS exhibits high sensitivity and efficient adsorption for tetracycline hydrochloride with 0.22 µm detection limit and ≈0.6 g g−1 removal capacity. To the best of the knowledge, this work is the first example of constructing Zr‐MOFs using pentacarboxylic acids as organic linkers and the first report of Zr‐MOFs with coexisted Zr6 connectivities in a single MOF matrix. This study provides a novel insight for the construction of Zr‐MOFs with unprecedented structures, which will not only enrich the structure diversity but also offer more opportunity to extend the applications of Zr‐MOFs. Four zirconium‐pentacarboxylate frameworks are successfully constructed with two novel underlying nets, where coexisted 4‐ and 9‐connected Zr6 clusters are formed in single MOF matrix. By changing the acceptor groups, the emission of resultant Zr‐MOFs can be customized from blue, yellow–green to red. The nano‐sized HIAM‐4053‐NS can be used for efficient detection and removal of tetracycline hydrochloride.