Radical Cage Effects: The Prediction of Radical Cage Pair Recombination Efficiencies Using Microviscosity Across a Range of Solvent Types

This study reports a method for correlating the radical recombination efficiencies (F-cp) of geminate radical cage pairs to the properties of the solvent. Although bulk viscosity (macroviscosity) is typically used to predict or interpret radical recombination efficiencies, the work reported here shows that microviscosity is a much better parameter. The use of microviscosity is valid over a range of different solvent system types, including nonpolar, aromatic, polar, and hydrogen bonding solvents. In addition, the relationship of F-cp to microviscosity holds for solvent systems containing mixtures of these solvent types. The microviscosities of the solvent systems were straightforwardly determined by measuring the diffusion coefficient of an appropriate probe by NMR DOSY spectroscopy. By using solvent mixtures, selective solvation was shown to not affect the correlation between Fcp and microviscosity. In addition, neither solvent polarity nor radical rotation affects the correlation between Fa and the microviscosity.