Customizing Photoredox Properties of PXX‐based Dyes through Energy Level Rigid Shifts of Frontier Molecular Orbitals

Here we describe the synthesis of electron-rich PXX derivatives in which the energy levels of the excited states have been tailored through the insertion of imide groups. This has allowed the development of a new series of oxygen-doped photoredox-active chromophores with improved oxidizing and reducing properties. Capitalizing on the dehalogenation of organic halides as a model reaction, we could investigate the photooxidative and photoreductive potential of these molecules in model chemical transformations. This prompted us to consider the first chemoselective transformation protocol, in which two different C-Br bonds could be chemoselectively reacted through the sequential photoactivation of two different colorants.