Binuclear, ruthenium - manganese complexes as simple artificial models, for photosystem II in green plants

Licheng Sun, Helena Berglund, Roman Davydov, Thomas Norrby, Leif Hammarström, Peter Korall, Anna Börje, Christian Philouze, Katja Berg, Anh Tran, Michael Andersson, Gunnar Stenhagen, Jerker Mårtensson, Mats Almgren, Stenbjörn Styring, Björn Åkermark

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Abstract

As part of a project aimed at developing models for photosystem II (PSII) in green plants, we have prepared a series of model compounds (7, 8, and 13). In these compounds, a photosensitizer, ruthenium(II) tris(bipyridyl) complex (to mimic the function of P680 in PSII), was covalently linked to a manganese(II) ion through different bridging ligands. The structures of the compounds were characterized by electron paramagnetic resonance measurements and electrospray ionization mass spectrometry. The interaction between the ruthenium and manganese moleties within the complex was probed by steady- state and time-resolved emission measurements. When the binuclear complexes are exposed to flash photolysis in the presence of an electron acceptor such as methylviologen (MV2+), it could be shown that after the initial electron transfer from the excited state of Ru(II) in compound 7, forming Ru(III) and MV+. , an intramolecular electron transfer from coordinated Mn(II) to the photogenerated Ru(III) occurred with a first-order rate constant of 1.8 x 105 s-1, regenerating Ru(II). This is believed to be the first supramolecular system where a manganese complex has been used as an electron donor to a photo-oxidized photosensitizer. Possible extensions to develop the manganese donor, and thus to approach the function of reaction center in PSII, are indicated.

Original languageEnglish
Pages (from-to)6996-7004
Number of pages9
JournalJournal of the American Chemical Society
Volume119
Issue number30
DOIs
Publication statusPublished - Jul 30 1997

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ASJC Scopus subject areas

  • Chemistry(all)

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