The high fluorescence sensitivity property and quenching mechanism of one-dimensional Cd-HCIA-1 sensor for nitrobenzene

Abstract

The sensing of nitroaromatic compounds in aqueous solution is closely related to environmental sustainability and human health. In this study, a novel Cd(II) coordination polymer (Cd-HCIA-1) was designed and prepared, and its crystal structure, luminescence performance, detection of nitro pollutants in water, and fluorescence quenching mechanisms were studied. Cd-HCIA-1 exhibited a one-dimensional ladder-like chain based on a T-shape ligand of 5-((4-carboxybenzyl) oxy) isophthalic acid (5-H₃CIA). The H-bonds and π–π stacking interactions were then used to construct the supramolecular skeleton in common. Luminescence studies revealed that Cd-HCIA-1 can detect nitrobenzene (NB) in aqueous solution with high sensitivity and selectivity, and the limit of detection was 3.03 × 10⁻⁹ mol L⁻¹. The fluorescence quenching mechanism of the photo-induced electron transfer for NB by Cd-HCIA-1 was obtained through an investigation of the pore structure, density of states, excitation energy, orbital interactions, hole–electron analysis, charge transfer, and electron transfer spectra by using density functional theory (DFT) and time-dependent DFT methods. NB was absorbed in the pore, π–π stacking increased the orbital overlap, and the LUMO was mainly composed of NB fragments. The charge transfer between ligands was blocked, resulting in fluorescence quenching. This study on fluorescence quenching mechanisms can be used to develop efficient explosive sensors.