Spectroscopic and structural study of complexes of quercetin with Al(III)

Complex formation between aluminium and quercetin (Q) in methanol was studied by the combined use of spectroscopic measurements and quantum chemical calculations. Quercetin presents in its structure three possible chelating sites in competition. UV–visible spectroscopy has showed the successive formation of two complexes of stoichiometry Al(III):Q of 1:2 and 2:1, respectively. The first site involved in the complex formation process is the 3-hydroxychromone and the second one is the ortho-dihydroxyl group. Semiempirical treatment, using the AM1 hamiltonian, permitted calculation of the structural modifications engendered by the ligand through chelation of one then two aluminium ions. The electronic and vibrational spectra have been calculated with the same method in order to compare them to the experimental spectra and so confirm the involved chelating sites. The simulated electronic spectra obtained from the complex models are in good agreement with the experimental UV–visible absorption spectra. In the same way the vibrational spectra of the complexes validate the proposed complex formation mechanism. The pH influence on the complexes stoichiometry and on the preferentially occupied chelating sites has been also investigated.