Synthesis and EPR study of Ru-Mn dimer complexes as catalysts for light-driven water oxidation: Towards solar energy conversion into fuels

Licheng Sun, Anh Tran, Yunhua Xu, Reiner Lomoth, Ping Huang Kenéz, Ann Magnuson Styring, Björn Åkermark, Leif Hammarström, Stenbjörn Styring

Research output: Contribution to journalConference articlepeer-review


In Photosystem II (PSII), solar energy is used to extract the electrons needed to reduce CO2 (the greenhouse gas) from water. Water oxidation is catalyzed by a domain within PSII called the water oxidizing complex (WOC), which involves a tyrosine residue. To mimic the WOC and the redox reactions involved in photosynthetic water oxidation, principles from PSII into supramolecular complexes were incorporated. To increase the similarities between supramolecular complexes and the donor side of PSII, a triad system complex 2 containing a RuII(bpy)3 center coupled via a modified L-tyrosine to a Mn2II,II-bpmp dimer (1) (bpmp = 2,6-bis[[ N,N-di .(2-pyridylmethyl)amino]methyl]-4-methylphenol) was synthesized. The photochemistry and electrochemistry in two model (complexes complex 1 and 2) were investigated. Both complexes underwent photo-induced, stepwise manganese oxidation by electron transfer to a photosensitizer. In the presence of water, the Mn2II,II moiety was successively oxidized to the mixed-valence Mn2III,IV state. Electrochemical studies indicated that ligand exchange in the Mn2III,III state, e.g., substitution of the acetate bridges by water molecules, was most likely a prerequisite for oxidation to the Mn2III,IV state. The light induced Ru oxidation to the highly oxidizing RuII species involves in oxidizing potential quite similar to that of P680+ in the PSII reaction center. The redox potentials of the different manganese oxidation states of 1 and 2 were also quite comparable to those involved in the donor side chemistry in PSII with the potential of the highest oxidation state remarkably close to that which is necessary for oxidizing water. The successive recovery of RuII accompanied by stepwise Mn oxidation, possibly mediated by the tyrosine derivative in 2, thereby, highly resembled important steps in the function of the WOC in PSII.

Original languageEnglish
Pages (from-to)300-303
Number of pages4
JournalACS Division of Fuel Chemistry, Preprints
Issue number1
Publication statusPublished - Mar 1 2002
Event224th ACS National Meeting - Orlando, FL, United States
Duration: Apr 7 2002Apr 11 2002

ASJC Scopus subject areas

  • Energy(all)

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