Reaction between diiodide anion radicals in ionic liquids

Takahashi, Kenji*; Sakai, Shingo*; Tezuka, Hiroaki*; Hiejima, Yusuke*; Katsumura, Yosuke; Watanabe, Masayoshi*

Photodetachment of electrons from iodide ions produced diiodide anion radicals in ionic liquids containing ammonium, pyrrolidinium, and piperidinium cations. The rates of reaction between diiodide anion radicals in molecular solvents such as HO, methanol, and ethanol could be estimated by the Debye-Smoluchowski equation, which accounts for electrostatic interactions using dielectric constants for the molecular solvents. In contrast, the rates of reaction between diiodide anion radicals in the ionic liquids were close to the diffusion limited rates for the neutral molecules, suggesting that electrostatic repulsion between the diiodide anion radicals is weakened by Coulombic shielding in the ionic liquids.