Photosensitizer-Free Singlet Oxygen Generation via Charge Transfer Transition involving Molecular O2 toward Highly Efficient Oxidative Coupling of Arylamines to Azoaromatics

Photosensitizer (PS)‐mediated generation of singlet oxygen, O2 (a1Δg) is a well‐explored phenomenon in chemistry and biology. However, the requirement of appropriate PS with optimum excited state properties is a prerequisite of this approach which limits its widespread application. Herein, we report the generation of O2 (a1Δg) via direct charge-transfer (CT) excitation of solvent‐O2 (X3Σ_g^-) collision complex without any PS and utilize it for the catalyst-free oxidative coupling of arylamines to azoaromatics under ambient conditions in aqueous medium. The electron paramagnetic resonance (EPR) spectroscopy revealed the formation of O2 (a1Δg) upon direct excitation with 370 nm light. The present approach shows broad substrate scope, fast reaction kinetics (90 min), high selectivity (100%), 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 via electron transfer (ET) from amines to O2 (a1Δg). 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 a way that molecular O2 simultaneously acts as a light absorbing chromophore (solvent‐O2 complex) as well as an efficient oxidant (O2 (a1Δg)) in the same reaction. This is the first report for 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 O2 (a1Δg) generated directly via CT excitation of solvent‐O2 complex toward various photochemical and photobiological transformations.