| Summary: | The free radical trapping capacities of multiple pyranoanthocyanins in wine storage and ageing were theoretically explored by density functional theory (DFT) methods. Intramolecular hydrogen bonds were detected in all pyranoanthocyanins, and the planarity of the compounds worsened with an increasing dielectric constant in the environment. Solvents significantly influenced the reaction enthalpies; thus, the preferred thermodynamic mechanisms of the free radical scavenging reactions were modified in different phases. This study incorporates hydrogen atom transfer (HAT), proton loss (PL), electron transfer (ET) reactions, and demethylation (De) of methoxy group mechanisms. The three pyranoanthocyanins have the capacity to capture n<sub>1</sub>+1 free radicals, where n<sub>1</sub> represents the number of methoxy groups. In the gas phase, they prefer employing the n<sub>1</sub>-De-HAT mechanism on the guaiacyl moiety of the B ring, resulting in the formation of a stable quinone or a quinone radical to scavenge free radicals. In the benzene phase, pyranoanthocyanins trap free radicals via a PL−n<sub>1</sub>−De−HAT mechanism. In the water phase, the targeted pyranoanthocyanins may dissociate in the form of carboxylate and tend to utilize the n<sub>2</sub>−PL−n<sub>1</sub>−De−ET mechanism, where n<sub>2</sub> and n<sub>1</sub> represent the number of phenolic groups and methoxy groups, respectively, facilitating multiple H<sup>+</sup>/e<sup>−</sup> reactions.
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