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

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 mu m detection limit and approximate to 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. image