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Issue 45, 2018
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Photoexcited state chemistry of metal–oxygen complexes

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Abstract

Recent advances on the excited state chemistry of metal–oxygen synthetic complexes based on earth-abundant metals such as copper, cobalt, and manganese are reviewed to show a much enhanced reactivity of the photoexcited states as compared with their relative ground states. Mononuclear copper(II)-superoxide and dinuclear copper(II)-peroxo complexes underwent copper–oxygen bond cleavage, dioxygen release, and copper(I)/dioxygen rebinding upon photoexcitation at low temperature. Photoirradiation of the cobalt–oxygen compound [(TAML)CoIV(O)]2− (6) (TAML = tetraamidomacrocyclic ligand) at 5 °C yielded a cobalt–oxygen excited state with 0.6(1) ns lifetime, showing a high reactivity in the bimolecular electron-transfer oxidations of m-xylene and anisole. An extremely long-lived excited state was generated upon photoexcitation of a manganese(IV)-oxo complex binding two Sc(OTf)3 molecules, which enabled the hydroxylation of benzene.

Graphical abstract: Photoexcited state chemistry of metal–oxygen complexes

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Publication details

The article was received on 05 Sep 2018, accepted on 08 Oct 2018 and first published on 09 Oct 2018


Article type: Frontier
DOI: 10.1039/C8DT03604G
Citation: Dalton Trans., 2018,47, 16019-16026
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    Photoexcited state chemistry of metal–oxygen complexes

    C. Saracini, S. Fukuzumi, Y. Lee and W. Nam, Dalton Trans., 2018, 47, 16019
    DOI: 10.1039/C8DT03604G

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