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A New Strategy for the Improvement of Photophysical Properties in Ruthenium(II) Polypyridyl Complexes: Synthesis and Photophysical and Electrochemical Characterization of Six Mononuclear Ruthenium(II) Bisterpyridine-Type Complexes
Uppsala University, Disciplinary Domain of Science and Technology, För teknisk-naturvetenskapliga fakulteten gemensamma enheter, Accelerator mass spectrometry group. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical Chemistry.
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2005 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 44, no 9, 3215-3225 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
ACS , 2005. Vol. 44, no 9, 3215-3225 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-95084DOI: 10.1021/ic048247aPubMedID: 15847430OAI: oai:DiVA.org:uu-95084DiVA: diva2:169160
Available from: 2006-11-09 Created: 2006-11-09 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Tuning of the Excited State Properties of Ruthenium(II)-Polypyridyl Complexes
Open this publication in new window or tab >>Tuning of the Excited State Properties of Ruthenium(II)-Polypyridyl Complexes
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Processes where a molecule absorbs visible light and then converts the solar energy into chemical energy are important in many biological systems, such as photosynthesis and also in many technical applications e.g. photovoltaics. This thesis describes a part of a multidisciplinary project, aiming at a functional mimic of the natural photosynthesis, with the overall goal of production of a renewable fuel from sun and water. More specific, the thesis is focused on design and photophysical characterization of new photosensitizers, i.e. light absorbers that should be capable of transferring electrons to an acceptor and be suitable building blocks for supramolecular rod-like donor-photosensitizer-acceptor arrays.

The excited state lifetime, the excited state energy and the geometry are important properties for a photosensitizer. The work presented here describes a new strategy to obtain longer excited state lifetimes of the geometrically favorable Ru(II)-bistridentate type complexes, without a concomitant substantial decrease in excited state energy. The basic idea is that a more octahedral coordination around the Ru will lead to longer excited state lifetimes. In the first generation of new photosensitizers a 50-fold increase of the excited state lifetime was observed, going from 0.25 ns for the model complex to 15 ns for the best photosensitizer. The second generation goes another step forward, to an excited state lifetime of 810 ns. Furthermore, the third generation of new photosensitizers show excited state lifetimes in the 0.45 - 5.5 microsecond region at room temperature, a significant improvement. In addition, the third generation of photosensitizers are suitable for further symmetric attachment of electron donor and acceptor motifs, and it is shown that the favorable properties are maintained upon the attachment of anchoring groups. The reactivity of the excited state towards light-induced reactions is proved and the photostability is sufficient so the new design strategy has proven successful.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2006. 79 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 237
Keyword
Physical chemistry, Artificial photosynthesis, Ruthenium(II), Bistridentate complexes, Excited state lifetime, Linear donor-photosenstizer-acceptor arrays, Temperature dependence, Excited state decay, Fysikalisk kemi
Identifiers
urn:nbn:se:uu:diva-7230 (URN)91-554-6707-5 (ISBN)
Public defence
2006-12-01, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:30
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Available from: 2006-11-09 Created: 2006-11-09 Last updated: 2011-06-10Bibliographically approved

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Abrahamsson, MariaJohansson, OlofBergquist, JonasHammarström, Leif

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