Journal
ACS CENTRAL SCIENCE
Volume 3, Issue 5, Pages 372-380Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscentsci.7b00125
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Funding
- Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Energy Biosciences, Department of Energy [DE-FG02-03ER15393]
- Center for Molecular Electrocatalysis, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences
- National Science Foundation Graduate Research Fellowship Grant [DGE-1144245]
- AFOSR through a Basic Research Initiative (BRI) grant [FA9550-12-1-0414]
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Nature employs a Tyr(z)-His pair as a redox relay that couples proton transfer to the redox process between P680 and the water oxidizing catalyst in photosystem II. Artificial redox relays composed of different benzimidazole phenol dyads (benzimidazole models His and phenol models Tyr) with substituents designed to simulate the hydrogen bond network surrounding the Tyr(z)-His pair have been prepared. When the benzimidazole substituents are strong proton acceptors such as primary or tertiary amines, theory predicts that a concerted two proton transfer process associated with the electrochemical oxidation of the phenol will take place. Also, theory predicts a decrease in the redox potential of the phenol by similar to 300 mV and a small kinetic isotope effect (KIE). Indeed, electrochemical, spectroelectrochemical, and KIE experimental data are consistent with these predictions. Notably, these results were obtained by using theory to guide the rational design of artificial systems and have implications for managing proton activity to optimize efficiency at energy conversion sites involving water oxidation and reduction.
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