Electronic spectroscopic characterization of the formation of iron(III) metal complexes: The 8-HydroxyQuinoline as ligand case study.

Synthetic siderophores derivated from 8-HydroxyQuinoline (HQ) present various biological and pharmacological activities, such as anti-neurodegenerative or anti-oxydative. However, their affinity towards iron(III) seems to depend on the position (i.e., 7 or 2) of the HQ substitution by an electron withdrawing group. Two ester-derivatives of HQ at 2- and 7-position are synthesized and their respective iron-complexation is characterized by a joined experimental and theoretical work. By investigating the stability of all the possible accessible spin states of the iron(III) complexes at density-functional theory (DFT) level, we demonstrate that the high-spin (HS) state is the most stable one, and leads to a UV/vis absorption spectrum in perfect match with experiments. From this DFT protocol, and in agreement with the experimental results, we show that the ester functionalization of HQ in 2-position weakens the formation of the iron(III) complex while its substitution in 7-position allows a salicylate coordination of the metal very close to the ideal octahedral environment.