Dynamic solvent effects in radical-radical coupling reactions: an almost bottleable localised singlet diradical.

Localised singlet diradicals are key intermediates in bond homolysis, which plays a crucial role in chemical reactions. However, thorough experimental analyses of the reaction dynamics and chemical properties are generally difficult because bond formation is rapid, even under low-temperature matrix conditions. In this study, the effects of solvent and pressure on the lifetimes of long-lived singlet diradicals with bulky substituents were investigated. The solvent dynamic effect was revealed to provide control over the rate constant of radical-radical coupling reactions, and an almost bottleable singlet diradical with a lifetime of ∼2 s at 293 K was obtained.