Photosensitizer-free singlet oxygen generation a charge transfer transition involving molecular O toward highly efficient oxidative coupling of arylamines to azoaromatics.

Photosensitizer (PS)-mediated generation of singlet oxygen, O (aΔ) is a well-explored phenomenon in chemistry and biology. However, the requirement of appropriate PSs with optimum excited state properties is a prerequisite for this approach which limits its widespread application. Herein, we report the generation of O (aΔ) direct charge-transfer (CT) excitation of the solvent-O (XΣ ) collision complex without any PS and utilize it for the catalyst-free oxidative coupling of arylamines to azoaromatics under ambient conditions in aqueous medium. Electron paramagnetic resonance (EPR) spectroscopy revealed the formation of O (aΔ) upon direct excitation with 370 nm light. The present approach shows broad substrate scope, remarkably fast reaction kinetics (90 and 40 min under an open and O atm, respectively), high selectivity (100%), and excellent yields (up to 100%), and works well for both homo- and hetero-coupling of arylamines. The oxidative coupling of arylamines was found to proceed through the generation of amine radicals electron transfer (ET) from amines to O (aΔ). Notably, electron-rich amines show higher yields of azo products compared to electron-deficient amines. Detailed mechanistic investigations using various spectroscopic tools revealed the formation of hydrazobenzene as an intermediate along with superoxide radicals which subsequently transform to hydrogen peroxide. The present study is unique in the way that molecular O simultaneously acts as a light-absorbing chromophore (solvent-O complex) as well as an efficient oxidant (O (aΔ)) in the same reaction. This is the first report on the efficient, selective, and sustainable synthesis of azo compounds in aqueous medium under an ambient atmosphere without any PCs/PSs and paves the way for further in-depth understanding of the chemical reactivity of O (aΔ) generated directly CT excitation of the solvent-O complex toward various photochemical and photobiological transformations.