Influence of Pb(II) ions on the EPR properties of the semiquinone radicals of humic acids and model compounds: high field EPR and relativistic DFT studies.

X-band (9.76 GHz) and high field (416.00 GHz) electron paramagnetic resonance spectroscopy (EPR) was used to study the interactions between Pb(II) ions and semiquinone radicals of natural humic acids and their simple models. The EPR experiments were performed on powder samples. The formation of Pb(II) complexes with the radicals was accompanied by a significant decrease of g parameters as compared to those observed for parent radicals. Two types of complexes were identified depending on the initial concentration of Pb(II) ions. For one of them the anisotropic hyperfine coupling with the (207)Pb nucleus was observed. Systematic DFT calculations were carried out for complexes with different forms of radical ligands (L(2)(-), HL(-), and H(2)L*) derived from 3,4-dihydroxybenzoic acid representing different ligation schemes. The g parameters calculated for the structure characterized by a significant accumulation of spin density on the Pb atom are strongly deviated from the values observed experimentally. Moreover, a decrease of the spin population on all oxygen atoms as a result of complexation of Pb(II) via carboxyl oxygens and protonation of hydroxyl oxygens is required to reproduce the experimental g parameters.