Spectroscopic properties of environmental relevant systems : 2’,3-dihydroxyflavone-ion complexes and polycyclic aromatic hydrocarbons : a joint experimental and theoretical study

Overview & Synopsis

This manuscript reports the results of an experimental and theoretical study of two molecular systems of environmental interest: 2',3-dihydroxyflavone (2'3HF) and polycyclic aromatic hydrocarbons (PAH). These systems were studied by a combination of electronic spectroscopic techniques (absorption and fluorescence) and quantum chemical calculations (DFT and TD-DFT). In the first part of this thesis, it is shown that 2'3HF has singular acid-base properties compared to other flavonols. The decrease of the pKa by several units is attributed to the presence of a hydrogen-bond network. In the excited state, an intramolecular proton transfer causes a dual fluorescence. An additional emission band, seemingly originating from a tautomeric form perturbed by interaction with the solvent, was revealed. Finally, an exhaustive study of the Ca(II), Mn(II) and Zn(II) complexes showed the formation of chelates with the α-hydroxyketone function. In the second part, three structural hypotheses to explain the experimental observation of visible-range laser-induced fluorescence (LIF) were explored. A study of van der Waals (vdW) dimers of PAHs provided insights into the nature of the monomer interaction and highlighted the difficulty of modelling these systems. However, the calculated electronic transitions suggest that these species cannot be responsible for the LIF signals. Secondly, an identical study of aliphatically bridged PAHs showed very similar results to vdW dimers, ruling out their involvement in the observed fluorescence. Finally, the hypothesis of emission from PAH radicals was explored. The latter is very promising and opens the way for further experimental and theoretical studies.