Closer to Photosystem II: A Co4O4 Cubane Catalyst with Flexible Ligand Architecture

We introduce the novel Co4O4 complex [Co-4(II)(hmp)(4)(mu-OAc)(2)(mu(2)-OAc)(2)(H2O)(2)] (1) (hmp = 2-(hydroxymethyl)pyridine) as the first Co(II)-based cubane water oxidation catalyst. Monodentate acetate and aqua ligands lend the flexible environment of 1 closest resemblance to photosystem II among its tetranuclear mimics to date. Visible-light-driven catalytic activity of 1 increases with pH value through aqua ligand deprotonation. The Co(II) core combines robustness and stability with flexibility through a new type of water-oxidation mechanism via mobile ligands.