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

Photoredox catalysis typically relies on the use of single chromophores, whereas strategies, in which two different light absorbers are combined, are rare. In photosystems I and II of green plants, the two separate chromophores P680 and P700 both absorb light independently of one another, and then their excitation energy is combined in the so-called Z-scheme, to drive an overall reaction that is thermodynamically very demanding. Here, we adapt this concept to perform photoredox reactions on organic substrates with the combined energy input of two red photons instead of blue or UV light. Specifically, a CuI bis(α-diimine) complex in combination with in situ 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.