Light‐Induced Electron Transfer in Manganese(V)–Oxo Corroles

Abstract

Electron and proton transfer reactions are essential elements in water oxidation by the oxygen‐evolving complex of photosystem II. To date manganese(V)–oxo corrole has successfully mimicked the oxygen evolution reaction. We report here ultrafast intramolecular electron transfer (ET) in corrole manganese (Mn) complexes. With femtosecond spectroscopy, the evolutions of transient absorption spectra of three kinds of Mn(V)–oxo corroles were measured. A ∼0.17 ps ET process has been observed in (OHF10C)MnV(O) after photoexcitation at 400 nm, which is absent for (F15C)MnV(O) and (F10C)MnV(O). The back ET is different from that of Mn(III) corrole ((OHF10C)MnIII), being a ∼12.3 ps ET followed by a very long ground‐state recovery. The mechanism of the ET observed in (OHF10C)MnV(O) has been discussed. The result reveals that the natural O−O bond formation may include ultrafast ET among the calcium‐ligated hydroxide, Mn(V), and the oxygen bound to the metal ion.