Towards an artificial model for Photosystem II: A manganese(II,II) dimer covalently linked to ruthenium(II) tris-bipyridine via a tyrosine derivative

Licheng Sun, Mary Katherine Raymond, Ann Magnuson, Denis Legourriérec, Markus Tamm, Malin Abrahamsson, Ping Huang Kenéz, Jerker Mårtensson, Gunnar Stenhagen, Leif Hammarström, Stenbjörn Styring, Björn Åkermark

Research output: Contribution to journalArticle

66 Citations (Scopus)

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 languageEnglish
Pages (from-to)15-22
Number of pages8
JournalJournal of Inorganic Biochemistry
Volume78
Issue number1
DOIs
Publication statusPublished - Jan 15 2000

Fingerprint

Photosystem II Protein Complex
Ruthenium
Manganese
Dimers
Tyrosine
Electrons
Derivatives
Photosensitizing Agents
Excited states
Viridiplantae
Electrospray ionization
Electrospray Ionization Mass Spectrometry
Photolysis
Electron Spin Resonance Spectroscopy
Mass spectrometry
Paramagnetic resonance
Rate constants
Ions
Oxidation

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 journalArticle

Sun, L, Raymond, MK, Magnuson, A, Legourriérec, D, Tamm, M, Abrahamsson, M, Huang Kenéz, P, Mårtensson, J, Stenhagen, G, Hammarström, L, Styring, S & Åkermark, B 2000, 'Towards an artificial model for Photosystem II: A manganese(II,II) dimer covalently linked to ruthenium(II) tris-bipyridine via a tyrosine derivative', Journal of Inorganic Biochemistry, vol. 78, no. 1, pp. 15-22. https://doi.org/10.1016/S0162-0134(99)00200-7
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. / Towards an artificial model for Photosystem II : A manganese(II,II) dimer covalently linked to ruthenium(II) tris-bipyridine via a tyrosine derivative. In: Journal of Inorganic Biochemistry. 2000 ; Vol. 78, No. 1. pp. 15-22.
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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.",
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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

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KW - Artificial photosynthesis

KW - Electron transfer

KW - Manganese dimer complexes

KW - Photosystem II

KW - Ruthenium complexes

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