3D Zn^II-Based coordination polymer: Synthesis, structure and fluorescent sensing property for nitroaromatic compounds

A water-stable Zn^II-based coordination polymer (CP) with excellent photophysical behavior, namely [Zn₂L(atez)(H₂O)₂] (compound 1; H₃L = 4-(2',3'-dicarboxylphenoxy); atez = 5-aminotetrazole), was successfully prepared by the solvothermal reaction of Zn ions with a π-conjugated and semi-rigid multicarboxylate ligand H₃L in the presence of N-containing linker atez. Compound 1 displays a hierarchically pillared three-dimensional (3D) (3,4,5)-connected (4·6²) (4²·6⁴) (4³·6⁴·8³) net which is based on two-dimensional (2D) multicarboxylate- Zn^II layers strutted by the atez ligands. Sensing investigations of compound 1 reveal that this material can selectively and sensitively detect nitroaromatic compounds in water suspension through fluorescence quenching effect. In particular, it is worth noting that it shows highly specific detection of nitrobenzene (NB) and 2,4,6-trinitrophenol (TNP) with remarkable quenching constants (K_SV = 7.5 × 10⁴ M^-1 for NB and K_SV = 1.9 × 10⁵ M^-1 for TNP) and low limit of detection (LOD = 0.93 μM for NB and LOD = 0.36 μM for TNP). Investigations reveal that the probable mechanisms for such sensing processes are the concurrent presence of fluorescence resonance energy transfer (FRET) as well as photoinduced electron transfer (PET) between the CP and nitroaromatic molecules. This work not only offers an effective route to improve the application of fluorescent CPs but also provide one novel probable fluorescence probe for nitroaromatic compounds.