The photocatalytic oxidative coupling of aryl amines to selectively synthesize azoaromatic compounds has been realized. Multiple different photocatalysts can be used to perform the general reaction; however, Ir(dF-CF 3 -ppy) 2 (dtbpy) + , where dF-CF 3 -ppy is 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine and dtpby is 4,4′-tert-butyl-2,2′-bipyridine, showed the greatest range of reactivity with various amine substrates. Both electron-rich and -deficient amines can be coupled with yields up to 95% under an ambient air atmosphere. Oxygen was deemed to be essential for the reaction and is utilized in the regeneration of the photocatalyst. Fluorescence quenching and radical trap experiments indicate an amine radical coupling mechanism that proceeds through a hydrazoaromatic intermediate before further oxidation occurs to form the desired azoaromatic products.

Atomic layer deposition immobilizes molecular catalysts on solid supports, which prevents molecular deactivation pathways and leads to longer catalyst lifetimes in high aqueous content solvents.