Red Light-Based Dual Photoredox Strategy Resembling the Z-Scheme of Natural Photosynthesis

formed 9,10-dicyanoanthracenyl radical anion in the presence of excess diisopropylethylamine catalyzes ca. 50 dehalogenation and detosylation reactions. This dual photoredox approach seems useful because red light is less damaging and has a greater penetration depth than blue or UV radiation. UV-vis transient absorption spectroscopy reveals that the subtle change in solvent from acetonitrile to acetone induces a changeover in the reaction mechanism, involving either a dominant photoinduced electron transfer or a dominant triplet-triplet energy transfer pathway. Our study illustrates the mechanistic complexity in systems operating under multiphotonic excitation conditions, and it provides insights into how the competition between desirable and unwanted reaction steps can become more controllable.