The aggregation behaviors of organic radicals in polar fluorinated arenes

Abstract Polar fluorinated arenes can promote organic free radical reactions, which have attracted scientists’ interest in recent years. However, it is still unknown how these solvents interact weakly with organic radical molecules to influence their reactivity. In this study, we investigated how organic free radicals aggregate in five polar fluorocarbon solvents, and demonstrated that different substituents can influence their aggregation behaviors. In these solvents, small organic radicals with simple substituents maintain a homogeneous solution; however, radicals with substituents that form intermolecular hydrogen bonds or with long‐chain aliphatic hydrocarbons tend to aggregate in them, whereas substituents of long‐chain aliphatic hydrocarbons tend to promote aggregation better. The critical aggregation concentrations of these aggregates are measured by concentration‐dependent UV–visible spectroscopy. Their topological morphologies are all spherical based on TEM. The compactness and rotational motivation speed of radical molecules within these aggregates are determined by EPR spectroscopy. The particle sizes of these aggregates are determined by analyzing their cyclic voltammograms. Most excitingly, electrochemical experiments reveal that the aggregation behaviors of free radical molecules with intermolecular hydrogen bonds can significantly increase their catalytic rate for electro‐oxidizing benzyl alcohol in such a solvent. The results of this study indicate that in polar fluorinated arenes organic radical molecules’ aggregation behaviors are related to their structures. This may provide guidelines for regulating organic radical reactivity in these solvents in the future.