Photocatalytic water oxidation: tuning light-induced electron transfer by molecular Co4O4 cores.
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.
ITM-CNR and Department of Chemical Sciences, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
Serena
S
Berardi
Giuseppina
G
La Ganga
Mirco
M
Natali
Irene
I
Bazzan
Fausto
F
Puntoriero
Andrea
A
Sartorel
Franco
F
Scandola
Sebastiano
S
Campagna
Marcella
M
Bonchio