Zn(II)-Based Mixed-Ligand-Bearing Coordination Polymers as Multi-Responsive Fluorescent Sensors for Detecting Dichromate, Iodide, Nitenpyram, and Imidacloprid

Coordination polymers (CPs) are organo-inorganic porous materials consisting of metal ions or clusters and organic linkers. These compounds have attracted attention for use in the fluorescence detection of pollutants. Here, two Zn-based mixed-ligand-bearing CPs, [Zn₂(DIN)₂(HBTC^2-)₂] (CP-1) and [Zn(DIN)(HBTC^2-)]·ACN·H₂O (CP-2) (DIN = 1,4-di(imidazole-1-yl)naphthalene, H₃BTC = 1,3,5-benzenetricarboxylic acid, and ACN = acetonitrile), were synthesized under solvothermal conditions. CP-1 and CP-2 were characterized by single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and powder X-ray diffraction analysis. Solid-state fluorescence analysis revealed an emission peak at 350 nm upon excitation at 225 and 290 nm. Fluorescence sensing tests showed that CP-1 was highly efficient, sensitive, and selective for detecting Cr₂O₇^2- at 225 and 290 nm, whereas I^- was only detected well at an excitation of 225 nm. CP-1 detected pesticides differently at excitation wavelengths of 225 and 290 nm; the highest quenching rates were for nitenpyram at 225 nm and imidacloprid at 290 nm. The quenching process may occur via the inner filter effect and fluorescence resonance energy transfer.