Theoretical Assessment of the Selective Fluorescence Quenching of 1-Amino-8-naphthol-3,6-disulfonic Acid (H-Acid) Complexes with Zn2+, Cd2+, and Hg2+: A DFT and TD-DFT Study

Density functional theory (DFT) and time-dependent (TD)-DFT calculations at the PBE0/6-31++G** aug-cc-PVDZ (along with corresponding ECP for metal ions) level of theory were carried out to investigate the differences in structure, bonding, and fluorescence behavior of 1-amino-8-naphthol-3,6-disulfonic acid (H-acid) (1) when coordinated to Zn2+ (2), Cd2+ (3), and Hg2+ (4) in a simulated continuous aqueous media (PCM). Ground and excited state calculations were performed on all compounds in order to gain insight on their bonding properties, as well as on their photochemical behavior, since we previously reported that complexation of Hg2+ quenches the fluorescence properties of ligand (1), while at the same time exhibits a different coordination pattern than the two other remaining complexes. Changes in the excited states radiative lifetime upon coordination to different metals account for this selective quenching.