Radical anions of flavonoids.

Several representatives of natural flavonoids and their synthetic nitro-derivatives have been investigated by polarography and electron paramagnetic resonance (EPR) spectroscopy under electrochemical reduction in acetonitrile, dimethylformamide (DMF), dimethylsulfoxide (DMSO) or 1,2-dimethoxyethane. All the compounds studied are reduced in the first stage by one-electron transfer, apart from flavanone, which accepts two electrons simultaneously. However, the primary radical anions were detected by EPR spectroscopy only for 4'-nitroflavone. It was shown that radical anions of other flavonoids quickly dimerized. The analysis of the temperature dependence of the hyperfine interaction constants and broadening of lines in EPR spectra of 4'-nitroflavone radical anions has shown that the distribution of spin density is due to both the change of polarity of the medium and rotation of the nitrophenyl moiety. The assignment of hyperfine structure constants for the 4'-nitroflavone radical anion was confirmed by density functional theory (DFT) calculations.