In this study, we developed newmethodologies to synthesize hangman porphyrins, hangman corroles and studiedwater oxidation and hydrogen electrocatalysis with those compounds. Efficientmanagement of proton and electron inventories is essential to catalysisinvolving small-molecule substrates. Our interest in catalytic reactionsmediated by proton-coupled electron transfer (PCET) has let us to developsynthetic constructs where acid functionality is poised above ametallo-porphyrin active site. We have demonstrated that such constructsuniquely promote four electron reduction of O2 to H2Oover the competing two electron pathway. We now extend this methodology toHangman Porphyrin Xanthene (HPX) and Hangman Corroles Xanthene (HCX) platformsthat poise a basic functionality above a putative high-valent metal-oxofragment. We target highly fluorinated hagman scaffolds such that themetal-aquo/metal-oxo redox couple is raised above the water/peroxide couple. Weenvision that the fluorinated platforms will exhibit enhanced oxidativerobustness under the conditions of electrolysis.

Water splitting, H<sub>2</sub> electrocatalysis with hangman porphyrins and hangman corroles

239th National Meeting (2010)

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Water splitting, H2 electrocatalysis with hangman porphyrins and hangman corroles

Water splitting, H₂ electrocatalysis with hangman porphyrins and hangman corroles