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

Sun, L C; Berglund, H; Davydov, Roman; Norrby, T; Hammarström, L; Korall, P; Börje, A; Philouze, C; Berg, K and Tran, A, et al. (1997) In Journal of the American Chemical Society 119(30). p.6996-7004
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 P-680 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 moieties 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... (More)
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 P-680 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 moieties 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 10(5) 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. (Less)
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METHYL VIOLOGEN, ELECTRON-TRANSFER, OXYGEN EVOLUTION, SCHIFF-BASES, WATER, PHOTOSYNTHESIS, 2, 2'-BIPYRIDINE, SPECTROSCOPY, DERIVATIVES, OXIDATION
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Journal of the American Chemical Society
volume
119
issue
30
pages
6996 - 7004
publisher
The American Chemical Society
external identifiers
  • scopus:0030847092
ISSN
1520-5126
DOI
10.1021/ja962511k
language
English
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6b845225-de44-4f55-bc18-b2fa6ca38bdf (old id 127091)
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2007-07-06 16:07:16
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@article{6b845225-de44-4f55-bc18-b2fa6ca38bdf,
  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 P-680 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 moieties 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 10(5) 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.},
  author       = {Sun, L C and Berglund, H and Davydov, Roman and Norrby, T and Hammarström, L and Korall, P and Börje, A and Philouze, C and Berg, K and Tran, A and Andersson, M and Stenhagen, G and Mårtensson, J and Almgren, M and Styring, Stenbjörn and Åkermark, B},
  issn         = {1520-5126},
  keyword      = {METHYL VIOLOGEN,ELECTRON-TRANSFER,OXYGEN EVOLUTION,SCHIFF-BASES,WATER,PHOTOSYNTHESIS,2,2'-BIPYRIDINE,SPECTROSCOPY,DERIVATIVES,OXIDATION},
  language     = {eng},
  number       = {30},
  pages        = {6996--7004},
  publisher    = {The American Chemical Society},
  series       = {Journal of the American Chemical Society},
  title        = {Binuclear ruthenium-manganese complexes as simple artificial models for photosystem II in green plants},
  url          = {http://dx.doi.org/10.1021/ja962511k},
  volume       = {119},
  year         = {1997},
}