Reticular Structural Diversification of Zirconium Metal–Organic Frameworks Through Angular Ligand Configuration Control

Reticular chemistry offers practical guidelines for enlarging and enriching the arsenal of metal-organic frameworks (MOFs). However, reticular expansion to access mesoporous structures remains challenging due to limitations in achieving precise control over both the size and configuration during building units' extension. Herein, we combine ligand isomerization and functionalization strategies to regulate the ligand configuration by systematically replacing aryl C-H groups with N atoms, resulting in angular dicarboxylate ligands with various symmetries. The assembly between a 4,4'-(pyridine-2,6-diyl)dibenzoic acid ligand (1N, <i>C</i>₂ symmetry) and 12-connected Zr₆ cluster leads to the formation of a <i>pseudo</i> <b>ftw</b> topology framework (NU-2611), where one pair of nose-to-nose 1N ligands resembles a tetra-topic ligand. When a 6,6'-(1,3-phenylene)dinicotinic acid ligand (2N, <i>C</i>_S symmetry) was used, another <i>pseudo</i> <b>ftw</b> network NU-2612 was obtained with a 2-fold framework interpenetration. Interestingly, the planar [2,2':6',2″-terpyridine]-5,5″-dicarboxylic acid ligand (3N, <i>C</i>_2<i>V</i> symmetry) yielded an intriguing mesoporous Zr-MOF with <b>kag</b> topology. NU-2613 represents the first example of <b>kag</b> Zr-MOF designed to include large, well-defined mesopores. The diversity of these MOFs was further enhanced through post-synthetic metalation of linkers. Particularly, metalation of the chelating 3N ligand with Fe³⁺ in NU-2613 enables efficient catalytic transformation within the functionalized channels. This work contributes insight into the reticular expansion of Zr-MOFs by finely-tuning the ligand planarity, advancing the structure diversification of mesoporous frameworks for specific applications.