Series of TM-OFs as a Platform for Efficient Catalysis and Multifunctional Luminescence Sensing

Three novel porous transition-metal-organic frameworks (TM-OFs), formulated as [Co₃(DCPN)₂(μ₂-OH₂)₄(H₂O)₄](DMF)₂ (1), [Cd₃(DCPN)₂(μ₂-OH₂)₄(H₂O)₄](DMF)₂ (2), and [CdK(DCPN)(DMA)] (3), have been successfully prepared via solvothermal conditions based on a 5-(3',6'-dicarboxylic phenyl) nicotinic carboxylic acid (H₃DCPN) ligand. 1 and 2 both have the same porous 3D network structure with the point symbol of {4¹⁰·6¹⁴·8⁴}·{4⁵·6}₂ based on trinuclear ({Co₃} or {Cd₃}) clusters, indicating a one-dimensional porous channel, and possess excellent water and thermal stability; 3 also displays a porous 3D network structure with a 4-connected sra topology based on the heteronuclear metal cluster {CdK}. Complex 1 can be used to load Pd nanoparticles (Pd NPs) via a wetness impregnation strategy to obtain Pd@1. The reduction of nitrophenols (2-NP, 3-NP, 4-NP) by Pd@1 in aqueous solution shows outstanding conversion, excellent rate constants (k), and remarkable cycling stability due to the synergistic effect of complex 1 and Pd NPs. Luminescence sensing tests confirmed that 2 is a reliable multifunctional chemical sensor with high selectivity and sensitivity for low concentrations of Fe³⁺, Cr₂O₇^2-, CPFX, and NFX. Specifically, 2 shows a fluorescence enhancement behavior toward fluoroquinolone antibiotics (CPFX and NFX), which has not been reported previously in the literature. Moreover, the rational mechanism of fluorescence sensing was also systematically investigated by various detection means and theoretical calculations.