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A New Strategy for Improvement of Photophysical Properties in Ruthenium(II) Polypyridyl Complexes. Synthesis, Photophysical and Electrochemical characterisation of Six Mononuclear Ruthenium(II) Bisterpyridine Type Complexes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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2005 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 44, no 9, p. 3215-3225Article in journal (Refereed) Published
Abstract [en]

The synthesis and characterization of six ruthenium(II) bistridentate polypyridyl complexes is described. These were designed on the basis of a new approach to increase the excited-state lifetime of ruthenium(II) bisterpyridine-type complexes. By the use of a bipyridylpyridyl methane ligand in place of terpyridine, the coordination environment of the metal ion becomes nearly octahedral and the rate of deactivation via ligand-field (i.e., metal-centered) states was reduced as shown by temperature-dependent emission lifetime studies. Still, the possibility to make quasi-linear donor−ruthenium−acceptor triads is maintained in the complexes. The most promising complex shows an excited-state lifetime of τ = 15 ns in alcohol solutions at room temperature, which should be compared to a lifetime of τ = 0.25 ns for [Ru(tpy)2]2+. The X-ray structure of the new complex indeed shows a more octahedral geometry than that of [Ru(tpy)2]2+. Most importantly, the high excited-state energy was retained, and thus, so was the potential high reactivity of the excited complex, which has not been the case with previously published strategies based on bistridentate complexes.

Place, publisher, year, edition, pages
2005. Vol. 44, no 9, p. 3215-3225
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-23637DOI: 10.1021/ic048247aISI: 000228813400036OAI: oai:DiVA.org:su-23637DiVA, id: diva2:193620
Available from: 2005-03-23 Created: 2005-03-23 Last updated: 2022-02-25Bibliographically approved
In thesis
1. Ruthenium(II) Polypyridyl Complexes in Supramolecular Systems relevant to Artificial Photosynthesis
Open this publication in new window or tab >>Ruthenium(II) Polypyridyl Complexes in Supramolecular Systems relevant to Artificial Photosynthesis
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes the synthesis and properties of ruthenium complexes relevant to artificial photosynthesis. The work includes preparation of RuIIpolypyridine complexes as well as multi component systems where RuII(bpy)3 or RuII(tpy)2 type complexes are used as photosesnsitizers.

In the first part, the synthesis and characterisation of bipyridyl(pyridyl)methane type ligands and the corresponding ruthenium(II) bistridentate polypyridyl complexes is described. The bipyridyl-pyridyl methane type ligands were designed to increase the excited state lifetime of ruthenium(II) bisterpyridine-type complexes by altering the ligand field as compared to normal terpyridine ligands.

In the second part photoinduced electron transfer and formation of charge separated states in donor-photosensitizer dyads or donor-photosensitizer-acceptor triads is studied. The first covalently linked donor-photosensitizer-acceptor triad with tyrosine as electron donor was prepared, and long lived light induced charge separation was observed. RuIIterpyridine complexes linked to carotenoid or tyrosine were also prepared, for studies of light induced charge separation on a TiO2 surface. Tryptofan was covalently linked to Ru(bpy)3 and proton coupled electron transfer from tryptophan to photogenerated ruthenium(III) was demonstrated. A pH-dependent study of the electron transfer rate gave insight into the mechanism of proton coupled electron transfer in amino acids.

Finally, the last part of the thesis presents the preparation and properties of the first complex containing a photosensitizer covalently linked to a Fe-hydrogenase active site model.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2005. p. 54
Keywords
Ruthenium complexes
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-417 (URN)91-7155-031-3 (ISBN)
Public defence
2005-04-18, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
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Available from: 2005-03-23 Created: 2005-03-23 Last updated: 2014-02-24Bibliographically approved

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