Photophysical and density functional studies of the interaction of a flavone derivative with the halides

Abstract

The synthesis, photophysical behavior, and anion-sensing ability of a fluorescent molecular system, N-(3-methoxy-4-oxo-2-phenyl-4H-chromen-7-yl)-benzamide (1H), designed and developed with a view to sensing fluoride ions, are reported. NMR and density functional studies on the system have been carried out to determine the nature of the interaction between 1H and X⁻ (X = halogen atom) responsible for fluoride-induced dramatic changes in the absorption and emission properties of 1H. The color change of 1H, which can be observed by the naked eye, is found specific to fluoride ion; it is unaffected by the presence of a large excess of Cl⁻, Br⁻, and I⁻, thus rendering 1H as a selective fluoride ion sensor in micromolar concentration in the visible region. The changes in the fluorescence behavior of 1H, specifically, the formation of an additional long-wavelength emission band in the presence of fluoride ion, allow ratiometric fluorescence signaling of the fluoride ion as well. The results suggest that abstraction of the acidic proton of 1H by the F⁻ leading to the formation of 1⁻ is responsible for the spectral changes that allow signaling of the F⁻. Density functional calculations of the optimized geometrical parameters and charge densities of the 1H···halide complexes confirm the proton abstraction mechanism of the signaling of F⁻. Calculations of the transition energies of the 1H, 1⁻, and 1H···F⁻ (hydrogen-bonded complex) show that only 1⁻ is responsible for the long-wavelength absorption and emission band observed in the presence of F⁻.