A hydrostable Zn2+ coordination polymer for multifunctional detection of inorganic and organic contaminants in water

Abstract

From the perspective of human health and environmental safety, the development of hydrostable fluorescent sensors for the detection of heavy metal ions and nitroaromatics is an important but a challenging issue. To this end, a water-stable Zn²⁺ coordination polymer formulated as {[Zn(H₂L)]·2DMF·3H₂O}_n (ZnCP) was prepared elaborately by a solvothermal method using a multidentate ligand (H₄L) with 2,6-pyridine-dicarboxylic acid spaced by para-substituted benzene. Single-crystal analysis shows that the new ZnCP exhibits one-dimensional chain structural features, which further promoted to afford a wrinkled two-dimensional network structure via inter-chain hydrogen bonding. Powder X-ray diffraction and fluorescence measurements show that it can maintain crystallinity and structural integrity under harsh acidic and alkaline conditions with the pH ranging from 4 to 11. Notably, the bright blue–emissive ZnCP showed selective fluorescence quenching effects for Fe³⁺ and picric acid (PA), which makes it an excellent chemical sensor for Fe³⁺ and picric acid (PA) with low detection limits of 0.41 and 0.26 μM in water. The recognition mechanism of Fe³⁺ could be attributed to UV absorption competition and resonance energy transfer in the aid of weak electrostatic interactions, while the recognition mechanism of PA is considered to be a multi-quenching mechanism dominated by absorption competition and PET effects with the assistance of hydrogen bonding. In addition, poly(methyl methacrylate) (PMMA) films doped with ZnCP (ZnCP@PMMA) were developed to provide better sensing performance and portability for practical applications.