Visible-light-responsive multielectron redox catalysis of lacunary polyoxometalates induced by substrate coordination to their lacuna.

We describe herein the efficient visible-light-responsive polyoxometalate-based multielectron photoredox catalysis induced by in situ coordination of alcohols to the lacuna of TBA4 H4 [γ-SiW10 O36 ] (I, TBA=tetra-n-butylammonium). The coordination of alcohols to the lacuna of I generated a new highest occupied molecular orbital as the electron donor level and enabled the visible-light-responsive multielectron transfer from alcohols to I, which could be utilized for aerobic alcohol oxidation and one-pot synthesis of N-arylimines starting from nitroarenes and primary alcohols.