Density functional theory study of the structure–antioxidant activity of polyphenolic deoxybenzoins

• DFT have been employed to study the antioxidant activity of four polyphenolic DOBs.
• The HAT, SET–PT and SPLET mechanisms have been investigated.
• The calculated results matched well with experimental values.
• HAT is thermodynamically preferred mechanism in gas phase.
• SPLET represents the most probable reaction pathway in polar solvents.

Quantum chemical calculations based on the density functional theory (DFT) have been employed to study the relationship between the structure and the antioxidant activity of four polyphenolic deoxybenzoins (DOBs) in solvents and the gas phase. The three main working mechanisms, H-atom transfer (HAT), single electron transfer–proton transfer (SET–PT) and sequential proton loss electron transfer (SPLET) have been investigated. The calculated results closely matched experimental values. The results obtained prove that for the HAT mechanism, the most efficient system possessed ortho-dihydroxy functionality. The results suggested that HAT would be the most favourable mechanism for explaining the radical-scavenging activity of polyphenolic DOBs in the gas phase, whereas the SPLET mechanism is the thermodynamically favourable pathway in polar solvents.