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J Am Chem Soc. 2012 Jul 11;134(27):11104-7. doi: 10.1021/ja303951z. Epub 2012 Jun 28.

Photocatalytic water oxidation: tuning light-induced electron transfer by molecular Co4O4 cores.

Author information

1
ITM-CNR and Department of Chemical Sciences, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.

Abstract

Isostructural cubane-shaped catalysts [Co(III)(4)(μ-O)(4)(μ-CH(3)COO)(4)(p-NC(5)H(4)X)(4)], 1-X (X = H, Me, t-Bu, OMe, Br, COOMe, CN), enable water oxidation under dark and illuminated conditions, where the primary step of photoinduced electron transfer obeys to Hammett linear free energy relationship behavior. Ligand design and catalyst optimization are instrumental for sustained O(2) productivity with quantum efficiency up to 80% at λ > 400 nm, thus opening a new perspective for in vitro molecular photosynthesis.

PMID:
22716164
DOI:
10.1021/ja303951z

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