Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation

• Published in: Proceedings of the National Academy of Sciences - PNAS Vol. 109; no. 39; pp. 15578 - 15583
• Main Authors: Megiatto, Jackson D, Antoniuk-Pablant, Antaeres, Sherman, Benjamin D, Kodis, Gerdenis, Gervaldo, Miguel, Moore, Thomas A, Moore, Ana L, Gust, Devens
• Format: Journal Article
• Language: English
• Published: United States National Academy of Sciences 25.09.2012; National Acad Sciences
• Subjects: Absorption spectra; benzimidazole; catalysts; CHEMICAL APPROACHES TO ARTIFICIAL PHOTOSYNTHESIS: SOLAR FUELS SPECIAL FEATURE; Chlorophyll; Chlorophyll - chemistry; Dyadic relations; Electron transfer; Electron Transport; electron transport chain; Electrons; energy transfer; Fluorescence; histidine; Line spectra; Models, Chemical; nitrogen; Oxidation; Oxidation-Reduction; Oxygen; oxygen evolving complex; Photosynthesis; Photosystem II; Photosystem II Protein Complex - chemistry; Physical Sciences; Porphyrins; Protons; redox potential; spectral analysis; thermodynamics; tyrosine; Water - chemistry
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.1118348109

In the photosynthetic photosystem II, electrons are transferred from the manganese-containing oxygen evolving complex (OEC) to the oxidized primary electron-donor chlorophyll P680 •⁺ by a proton-coupled electron transfer process involving a tyrosine-histidine pair. Proton transfer from the tyrosine phenolic group to a histidine nitrogen positions the redox potential of the tyrosine between those of P680 •⁺ and the OEC. We report the synthesis and time-resolved spectroscopic study of a molecular triad that models this electron transfer. The triad consists of a high-potential porphyrin bearing two pentafluorophenyl groups (PF ₁₀), a tetracyanoporphyrin electron acceptor (TCNP), and a benzimidazole-phenol secondary electron-donor (Bi-PhOH). Excitation of PF ₁₀ in benzonitrile is followed by singlet energy transfer to TCNP (τ = 41 ps), whose excited state decays by photoinduced electron transfer (τ = 830 ps) to yield [Formula]. A second electron transfer reaction follows (τ < 12 ps), giving a final state postulated as BiH ⁺-PhO •-PF ₁₀-TCNP •⁻, in which the phenolic proton now resides on benzimidazole. This final state decays with a time constant of 3.8 μs. The triad thus functionally mimics the electron transfers involving the tyrosine-histidine pair in PSII. The final charge-separated state is thermodynamically capable of water oxidation, and its long lifetime suggests the possibility of coupling systems such as this system to water oxidation catalysts for use in artificial photosynthetic fuel production.