A biomimetic approach to artificial photosynthesis: Ru(II)-polypyridine photo-sensitisers linked to tyrosine and manganese electron donors

Leif Hammarström, Licheng Sun, Björn Åkermark, Stenbjörn Styring

Research output: Contribution to journalReview article

37 Citations (Scopus)

Abstract

The paper describes recent advances towards the construction of functional mimics of the oxygen evolving complex in photosystem II (PSII) that are coupled to photoinduced charge separation. Some key principles of PSII and artificial systems for light-induced charge accumulation are discussed. Systems are described where 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 photo-oxidised Ru(III) complex has been studied using optical flash photolysis and EPR experiments. A step-wise electron transfer Mn2(III,III) ⋺ tyrosine ⋺ Ru(III) has been demonstrated, in analogy to the reaction on the donor side of PSII. 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 reactions in PSII is made. Finally, light-induced oxidation of a manganese dimer linked to a Ru(II)-photosensitiser has been observed. Preliminary results suggest the possibility of photo-oxidising manganese dimers in several steps, which is an important advancement towards water oxidation.

Original languageEnglish
Pages (from-to)2145-2160
Number of pages16
JournalSpectrochimica Acta - Part A Molecular and Biomolecular Spectroscopy
Volume57
Issue number11
DOIs
Publication statusPublished - Jan 1 2001

    Fingerprint

Keywords

  • Artificial photosynthesis
  • Electron transfer
  • Manganese
  • Photochemistry
  • Photosystem II
  • Ruthenium

ASJC Scopus subject areas

  • Analytical Chemistry
  • Atomic and Molecular Physics, and Optics
  • Instrumentation
  • Spectroscopy

Cite this