Hydrogen is the most promising fuel of the future owing to its carbon-free, high-energy content and potential to be efficiently converted into either electrical or thermal energy. The greatest technical barrier to accessing this renewable resource remains the inability to create inexpensive catalysts for the solar-driven oxidation of water. To date, the most efficient system that uses solar energy to oxidize water is the photosystem II water-oxidizing complex (PSII-WOC), which is found within naturally occurring photosynthetic organisms. The catalytic core of this enzyme is a CaMn4Ox cluster, which is present in all known species of oxygenic phototrophs and has been conserved since the emergence of this type of photosynthesis about 2.5 billion years ago. The key features that facilitate the catalytic success of the PSII-WOC offer important lessons for the design of abiological water oxidation catalysts. In this Account, we examine the chemical principles that may govern the PSII-WOC by comparing the water oxidation capabilities of structurally related synthetic manganese-oxo complexes, particularly those with a cubical Mn4O4 core ("cubanes"). We summarize this research, from the self-assembly of the first such clusters, through the elucidation of their mechanism of photoinduced rearrangement to release O 2, to recent advances highlighting their capability to catalyze sustained light-activated electrolysis of water. The [Mn4O 4]6+ cubane core assembles spontaneously in solution from monomeric precursors or from [Mn2O2]3+ core complexes in the presence of metrically appropriate bidentate chelates, for example, diarylphosphinates (ligands of Ph2PO2 - and 4-phenyl- substituted derivatives), which bridge pairs of Mn atoms on each cube face (Mn4O4L6). The [Mn4O 4]6+ core is enlarged relative to the [Mn 2O2]3+ core, resulting in considerably weaker Mn-O bonds. Cubanes are ferocious oxidizing agents, stronger than analogous complexes with the [Mn2O2]3+ core, as demonstrated both by the range of substrates they dehydrogenate or oxygenate (unactivated alkanes, for example) and the 25% larger O-H bond enthalpy of the resulting μ3-OH bridge. The cubane core topology is structurally suited to releasing O2, and it does so in high yield upon removal of one phosphinate by photoexcitation in the gas phase or thermal excitation in the solid state. This is quite unlike other Mn-oxo complexes and can be attributed to the elongated Mn-O bond lengths and low-energy transition state to the μ-peroxo precursor. The photoproduct, [Mn4O2L 5]+, an intact nonplanar butterfly core complex, is poised for oxidative regeneration of the cubane core upon binding of two water molecules and coupling to an anode. Catalytic evolution of O2 and protons from water exceeding 1000 turnovers can be readily achieved by suspending the oxidized cubane, [Mn4O4L6] +, into a proton-conducting membrane (Nafion) preadsorbed onto a conducting electrode and electroxidizing the photoreduced butterfly complexes by the application of an external bias. Catalytic water oxidation can be achieved using sunlight as the only source of energy by replacing the external electrical bias with redox coupling to a photoanode incorporating a Ru(bipyridyl) dye.
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