Photoinduced Electron Transfer in Rhenium(I)−Oligotriarylamine Molecules

Two molecular triads with an oligotriarylamine multielectron donor were synthesized and investigated with a view to obtaining charge-separated states in which the oligotriarylamine is oxidized 2-fold. Such photoinduced accumulation of multiple redox equivalents is of interest for artificial photosynthesis. The first triad was comprised of the oligotriarylamine and two rhenium(I) tricarbonyl diimine photosensitizers each of which can potentially accept one electron. In the second triad the oligotriarylamine was connected to anthraquinone, in principle an acceptor of two electrons, via a rhenium(I) tricarbonyl diimine unit. With nanosecond transient absorption spectroscopy (using an ordinary pump–probe technique) no evidence for the generation of 2-fold oxidized oligotriarylamine or 2-fold reduced anthraquinone was found. The key factors limiting the photochemistry of the new triads to simple charge separation of one electron and one hole are discussed, and the insights gained from this study are useful for further research in the area of charge accumulation in purely molecular (nanoparticle-free) systems. An important problem of the rhenium-based systems considered here is the short wavelength required for photoexcitation. In the second triad, photogenerated anthraquinone monoanion is protonated by organic acids, and the resulting semiquinone species leads to an increase in lifetime of the charge-separated state by about an order of magnitude. This shows that the proton-coupled electron transfer chemistry of quinones could be beneficial for photoinduced charge accumulation.