Extremely slow and extremely fast new water oxidation catalysts based on the Ru-bda (bda= 2,2'-bipyridine-6,6'-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s(-1), respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system p-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.
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