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Reduction of aryl halides by consecutive visible light-induced electron transfer processes

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Science  07 Nov 2014:
Vol. 346, Issue 6210, pp. 725-728
DOI: 10.1126/science.1258232

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Doubling up on optically driven catalysis

During photosynthesis, plants absorb light from the Sun four consecutive times before they accumulate enough energy to make oxygen from water. In contrast, when chemists harness light energy to promote reactivity, they tend to rely on single discrete absorption events. Ghosh et al. now show that a particular dye molecule can channel the combined energy from two absorbed photons to the reduction and subsequent coupling reactions of aryl halide molecules. The method expands the reach of photocatalysis to a broader range of compounds, such as chlorides, which are too stable to breach with a single photon.

Science, this issue p. 725

Abstract

Biological photosynthesis uses the energy of several visible light photons for the challenging oxidation of water, whereas chemical photocatalysis typically involves only single-photon excitation. Perylene bisimide is reduced by visible light photoinduced electron transfer (PET) to its stable and colored radical anion. We report here that subsequent excitation of the radical anion accumulates sufficient energy for the reduction of stable aryl chlorides giving aryl radicals, which were trapped by hydrogen atom donors or used in carbon-carbon bond formation. This consecutive PET (conPET) overcomes the current energetic limitation of visible light photoredox catalysis and allows the photocatalytic conversion of less reactive chemical bonds in organic synthesis.

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