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Mimicking photosystem II reactions in artificial photosynthesis: Ru(II)-polypyridine photosensitisers linked to tyrosine and manganese electron donors

Hammarström, Leif ; Sun, Licheng ; Åkermark, Björn and Styring, Stenbjörn LU (2000) In Catalysis Today 58(2-3). p.57-69
Abstract
The paper describes a project aiming at constructing functional mimics of the oxygen evolving complex in photosystem II, coupled to photoinduced charge separation. Biomimetic electron donors, manganese complexes and tyrosine, have been linked to a Ru(II)-polypyridine photosensitiser. Oxidation of the donors by intramolecular electron transfer from the photooxidised Ru(III) complex was demonstrated using optical flash photolysis and EPR experiments. A step-wise electron transfer Mn(III,III)->tyrosine->Ru(III) was demonstrated, in analogy to the reaction on the donor side of photosystem II. Electron transfer from the tyrosine to Ru(III) was coupled to tyrosine deprotonation. This resulted in a large reorganisation energy and thus a... (More)
The paper describes a project aiming at constructing functional mimics of the oxygen evolving complex in photosystem II, coupled to photoinduced charge separation. Biomimetic electron donors, manganese complexes and tyrosine, have been linked to a Ru(II)-polypyridine photosensitiser. Oxidation of the donors by intramolecular electron transfer from the photooxidised Ru(III) complex was demonstrated using optical flash photolysis and EPR experiments. A step-wise electron transfer Mn(III,III)->tyrosine->Ru(III) was demonstrated, in analogy to the reaction on the donor side of photosystem II. Electron transfer from the tyrosine to Ru(III) was coupled to tyrosine deprotonation. This resulted in a large reorganisation energy and thus a slow reaction rate, unless the tyrosine was hydrogen bonded or already deprotonated. A comparison with analogous reaction in photosystem II is made. Finally, light-induced oxidation of a manganese dimer linked to a Ru(II)-photosensitiser was observed. Preliminary results suggest the possibility of photooxidising manganese dimers in several steps, which is an important step towards water oxidation. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Electron transfer, Manganese, Ruthenium, Photochemistry, Artificial photosynthesis, Photosystem II
in
Catalysis Today
volume
58
issue
2-3
pages
57 - 69
publisher
Elsevier
external identifiers
  • scopus:0033740821
ISSN
0920-5861
DOI
10.1016/S0920-5861(00)00242-X
language
English
LU publication?
yes
id
9314cf73-c8d6-4917-a4a9-0017d6e56855 (old id 125104)
date added to LUP
2016-04-01 15:28:10
date last changed
2022-01-28 05:32:33
@article{9314cf73-c8d6-4917-a4a9-0017d6e56855,
  abstract     = {{The paper describes a project aiming at constructing functional mimics of the oxygen evolving complex in photosystem II, coupled to photoinduced charge separation. Biomimetic electron donors, manganese complexes and tyrosine, have been linked to a Ru(II)-polypyridine photosensitiser. Oxidation of the donors by intramolecular electron transfer from the photooxidised Ru(III) complex was demonstrated using optical flash photolysis and EPR experiments. A step-wise electron transfer Mn(III,III)->tyrosine->Ru(III) was demonstrated, in analogy to the reaction on the donor side of photosystem II. Electron transfer from the tyrosine to Ru(III) was coupled to tyrosine deprotonation. This resulted in a large reorganisation energy and thus a slow reaction rate, unless the tyrosine was hydrogen bonded or already deprotonated. A comparison with analogous reaction in photosystem II is made. Finally, light-induced oxidation of a manganese dimer linked to a Ru(II)-photosensitiser was observed. Preliminary results suggest the possibility of photooxidising manganese dimers in several steps, which is an important step towards water oxidation.}},
  author       = {{Hammarström, Leif and Sun, Licheng and Åkermark, Björn and Styring, Stenbjörn}},
  issn         = {{0920-5861}},
  keywords     = {{Electron transfer; Manganese; Ruthenium; Photochemistry; Artificial photosynthesis; Photosystem II}},
  language     = {{eng}},
  number       = {{2-3}},
  pages        = {{57--69}},
  publisher    = {{Elsevier}},
  series       = {{Catalysis Today}},
  title        = {{Mimicking photosystem II reactions in artificial photosynthesis: Ru(II)-polypyridine photosensitisers linked to tyrosine and manganese electron donors}},
  url          = {{http://dx.doi.org/10.1016/S0920-5861(00)00242-X}},
  doi          = {{10.1016/S0920-5861(00)00242-X}},
  volume       = {{58}},
  year         = {{2000}},
}