Topological Diversity, Adsorption and Fluorescence Properties of MOFs Based on a Tetracarboxylate Ligand

The combination of a tetradentate ligand, N , N , N′ , N′ ‐benzidinetetrabenzoate (BenzTB), with paddle‐wheel SBUs based on Zn, Co or Cu has led to a series of new metal–organic frameworks (MOFs) with different structural motifs, depending on the additional acid present and the reaction temperature. Isomorphous compounds M 2 (H 2 O) 2 (BenzTB) [DUT‐10(M), M = Zn, Cu, Co] crystallize in the Imma space group (sp. gr.) and adopt the lvt topology, whereas the use of Zn and Cu under modified crystallization conditions gives rise to new phases Zn 2 (H 2 O) 2 (BenzTB) (sp. gr. Cccm , DUT‐11) and Cu 2 (H 2 O) 2 (BenzTB) (sp. gr. P 4/ mnc , DUT‐12) with pts and ssb framework topologies, respectively. DUT‐10(Zn) exhibits selective gas sorption properties for H 2 and CO 2 over N 2 and solvent‐induced change in fluorescence.