Pyrenoimidazolyl-Benzaldehyde Fluorophores: Synthesis, Properties, and Sensing Function for Fluoride Anions

Abstract

Two structural isomers of (9<i>H</i>-pyreno[4,5-<i>d</i>]imidazol-10-yl)-benzaldehyde, with para and meta substitution patterns, were synthesized by condensation of 4,5-pyrenedione with terephthalaldehyde and isophthalaldehyde, respectively. These new pyrenoimidazole derivatives were characterized by single-crystal X-ray crystallography, UV-vis absorption spectroscopy, fluorescence spectroscopy, and cyclic voltammetry to elucidate their structural, solid-state packing, and electronic properties. Interactions of these compounds with fluoride anions in polar organic solvents (acetone and dimethyl sulfoxide) were investigated by NMR, UV-vis, and fluorescence techniques in conjunction with density functional theory calculations. UV-vis analysis showed that the binding of the two pyrenoimidazolyl benzaldehydes with fluoride anions resulted in significant colorimetric responses, while fluorescence studies showed that the <i>para</i>-pyrenoimidazolyl benzaldehyde behaved as an intramolecular charge transfer fluorescent probe, exhibiting ratiometric sensing performance to efficiently detect and quantify fluoride anions at the sub-millimolar level.