Theoretical and experimental insights into the complexation of 8-hydroxyquinoline-5-sulfonate with divalent ions of Group 12 metals

The complexation of 8-hydroxyquinoline-5-sulfonic acid with cadmium(II) and mercury(II) has been studied in aqueous solutions using UV/visible absorption, fluorescence and H-1 NMR spectroscopy, accompanied by DFT calculations. Results are compared with the behavior of zinc(II) and show in all cases the dominant formation of a 1:2 (metal:ligand) complex. OFT calculations under PCM (water) conditions indicate a preference for hexacoordinated metal centers with two ligands and two water molecules. However, while the zinc(II) complex has a square bipyramidal geometry, with the two 8-HQS ligands and metal in the same plane and two coordinated water molecules mutually trans, with cadmium(II) and mercury(II), the isomers in which the water molecules are in the cis geometry are more stable. Changes in UV-Vis absorption, fluorescence spectra and fluorescence intensity are observed on complexation. Fluorescence quantum yields follow the order Zn/8-HQS < Cd/8-HQS > Hg/8-HQS. We believe two competing factors may be involved: an increase in fluorescence on going from Zn(II) to Cd(II) due to increased stability, and a decrease on going increasing atomic number of the metal ion due to the heavy atom effect which increases intersystem crossing. Triplet state quantum yields were measured for the Zn(II) and Cd(II) complexes, and the value for the cadmium(II) complex is higher, in agreement with the heavy atom effect. However, the sum of fluorescence and triplet quantum yields in these cases is less than unity. It is suggested that there is a competing non-radiative route for deactivation of the excited state through ligand or solvent exchange. This provides a ready explanation of increased fluorescence yields when meta1/8-HQS complexes are immobilized in solid matrices. (C) 2012 Elsevier Ltd. All rights reserved.