Abstract
In order to model the individual electron transfer steps from the manganese cluster to the photooxidized sensitizer P680 + in Photosystem II (PS II) in green plants, the supramolecular complex 4 has been synthesized. In this complex, a ruthenium(II) tris-bipyridine type photosensitizer has been linked to a manganese(II) dimer via a substituted L-tyrosine, which bridges the manganese ions. The trinuclear complex 4 was characterized by electron paramagnetic resonance (EPR) and electrospray ionization mass spectrometry (ESI-MS). The excited state lifetime of the the ruthenium tris-bipyridine moiety in 4 was found to be about 110 ns in acetonitrile. Using flash photolysis in the presence of an electron acceptor (methylviologen), it was demonstrated that in the supramolecular complex 4 an electron was transferred from the excited state of the ruthenium tris-bipyridine moiety to methylviologen, forming a methylviologen radical and a ruthenium(III) tris-bipyridine moiety. Next, the Ru(III) species retrieved the electron from the manganese(II/II) dimer in an intramolecular electron transfer reaction with a rate constant k(ET)>1.0x107 s-1, generating a manganese(II/III) oxidation state and regenerating the ruthenium(II) photosensitizer. This is the first example of intramolecular electron transfer in a supramolecular complex, in which a manganese dimer is covalently linked to a photosensitizer via a tyrosine unit, in a process which mimics the electron transfer on the donor side of PS II. Copyright (C) 1999 Elsevier Science Inc.
| Original language | English |
|---|---|
| Pages (from-to) | 15-22 |
| Number of pages | 8 |
| Journal | Journal of Inorganic Biochemistry |
| Volume | 78 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - Jan 15 2000 |
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Keywords
- Artificial photosynthesis
- Electron transfer
- Manganese dimer complexes
- Photosystem II
- Ruthenium complexes
ASJC Scopus subject areas
- Biochemistry
- Inorganic Chemistry
Cite this
Towards an artificial model for Photosystem II : A manganese(II,II) dimer covalently linked to ruthenium(II) tris-bipyridine via a tyrosine derivative. / Sun, Licheng; Raymond, Mary Katherine; Magnuson, Ann; Legourriérec, Denis; Tamm, Markus; Abrahamsson, Malin; Huang Kenéz, Ping; Mårtensson, Jerker; Stenhagen, Gunnar; Hammarström, Leif; Styring, Stenbjörn; Åkermark, Björn.
In: Journal of Inorganic Biochemistry, Vol. 78, No. 1, 15.01.2000, p. 15-22.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Towards an artificial model for Photosystem II
T2 - A manganese(II,II) dimer covalently linked to ruthenium(II) tris-bipyridine via a tyrosine derivative
AU - Sun, Licheng
AU - Raymond, Mary Katherine
AU - Magnuson, Ann
AU - Legourriérec, Denis
AU - Tamm, Markus
AU - Abrahamsson, Malin
AU - Huang Kenéz, Ping
AU - Mårtensson, Jerker
AU - Stenhagen, Gunnar
AU - Hammarström, Leif
AU - Styring, Stenbjörn
AU - Åkermark, Björn
PY - 2000/1/15
Y1 - 2000/1/15
N2 - In order to model the individual electron transfer steps from the manganese cluster to the photooxidized sensitizer P680 + in Photosystem II (PS II) in green plants, the supramolecular complex 4 has been synthesized. In this complex, a ruthenium(II) tris-bipyridine type photosensitizer has been linked to a manganese(II) dimer via a substituted L-tyrosine, which bridges the manganese ions. The trinuclear complex 4 was characterized by electron paramagnetic resonance (EPR) and electrospray ionization mass spectrometry (ESI-MS). The excited state lifetime of the the ruthenium tris-bipyridine moiety in 4 was found to be about 110 ns in acetonitrile. Using flash photolysis in the presence of an electron acceptor (methylviologen), it was demonstrated that in the supramolecular complex 4 an electron was transferred from the excited state of the ruthenium tris-bipyridine moiety to methylviologen, forming a methylviologen radical and a ruthenium(III) tris-bipyridine moiety. Next, the Ru(III) species retrieved the electron from the manganese(II/II) dimer in an intramolecular electron transfer reaction with a rate constant k(ET)>1.0x107 s-1, generating a manganese(II/III) oxidation state and regenerating the ruthenium(II) photosensitizer. This is the first example of intramolecular electron transfer in a supramolecular complex, in which a manganese dimer is covalently linked to a photosensitizer via a tyrosine unit, in a process which mimics the electron transfer on the donor side of PS II. Copyright (C) 1999 Elsevier Science Inc.
AB - In order to model the individual electron transfer steps from the manganese cluster to the photooxidized sensitizer P680 + in Photosystem II (PS II) in green plants, the supramolecular complex 4 has been synthesized. In this complex, a ruthenium(II) tris-bipyridine type photosensitizer has been linked to a manganese(II) dimer via a substituted L-tyrosine, which bridges the manganese ions. The trinuclear complex 4 was characterized by electron paramagnetic resonance (EPR) and electrospray ionization mass spectrometry (ESI-MS). The excited state lifetime of the the ruthenium tris-bipyridine moiety in 4 was found to be about 110 ns in acetonitrile. Using flash photolysis in the presence of an electron acceptor (methylviologen), it was demonstrated that in the supramolecular complex 4 an electron was transferred from the excited state of the ruthenium tris-bipyridine moiety to methylviologen, forming a methylviologen radical and a ruthenium(III) tris-bipyridine moiety. Next, the Ru(III) species retrieved the electron from the manganese(II/II) dimer in an intramolecular electron transfer reaction with a rate constant k(ET)>1.0x107 s-1, generating a manganese(II/III) oxidation state and regenerating the ruthenium(II) photosensitizer. This is the first example of intramolecular electron transfer in a supramolecular complex, in which a manganese dimer is covalently linked to a photosensitizer via a tyrosine unit, in a process which mimics the electron transfer on the donor side of PS II. Copyright (C) 1999 Elsevier Science Inc.
KW - Artificial photosynthesis
KW - Electron transfer
KW - Manganese dimer complexes
KW - Photosystem II
KW - Ruthenium complexes
UR - http://www.scopus.com/inward/record.url?scp=0034651173&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0034651173&partnerID=8YFLogxK
U2 - 10.1016/S0162-0134(99)00200-7
DO - 10.1016/S0162-0134(99)00200-7
M3 - Article
VL - 78
SP - 15
EP - 22
JO - Journal of Inorganic Biochemistry
JF - Journal of Inorganic Biochemistry
SN - 0162-0134
IS - 1
ER -