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

Abstract

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.