Fluorescence-quenching mechanisms of novel isomorphic Zn/Cd coordination polymers for selective nitrobenzene detection

Nitroaromatic compounds in aqueous undermine environmental sustainability and affect human health. The development of a fluorescent sensor capable of efficiently and selectively detecting trace amounts of nitroaromatic compounds presents a considerable challenge. This study introduced Zn/Cd isomeric coordination polymers (Zn-H2CIA-1/Cd-H2CIA-2), which are synthesized using 5-((4-carboxybenzyl)oxy)isophthalic acid (5-H3CIA) and 1,10-phenanthroline (Phen). The polymers have zero-dimensional discrete crystal structure with a six-coordinated scissor-like shape. The two coordination polymers can be used as fluorescent sensors for detecting nitrobenzene (NB) and demonstrated favorable sensitivity, with detection limits of 1.95 × 10-8 and 4.66 × 10-7 mol/L, respectively. Zn-H2CIA-1 exhibited stronger fluorescence and a more sensitive response to NB compared with Cd-H2CIA-2. To elucidate their fluorescence-quenching mechanisms, we analyzed Zn-H2CIA-1 by performing DFT and TD-DFT calculations. The pore structure, density of states, excitation energy, hole-electron distribution, and orbital composition were analyzed. The suitable size of pores in Zn-H2CIA-1 is the main reason for its high NB selectivity. Moreover, intermolecular π-π stacking interactions result in an orbital overlap between Zn-H2CIA-1 and NB, enabling the transfer of electrons from Zn-H2CIA-1 to NB. This electron transfer is identified as the fundamental cause of fluorescence quenching in Zn-H2CIA-1.