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The homogeneous systems [nBu4N]4[W10O32]/strong acid/acetonitrile/alkane is the first polymetallate system which makes possible a photo-redox chemistry—transformation of light into chemical energy—with high quantum yields. Alkanes are selectively photo-dehydrogenated by this system using UV light of low energy (λ > 360 nm); reaction 1 [RIGHTWARDS ARROW] 2 is typical.