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Vectorial Electron Transfer in Donor-Photosensitizer-Acceptor Triads Based on Novel Bis-tridentate Ruthenium Polypyridyl Complexes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
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2010 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 16, no 9, 2830-2842 p.Article in journal (Refereed) Published
Abstract [en]

The first examples of rodlikedonor–photosensitizer–acceptor arrays based on bis-2,6-di(quinolin-8-yl)pyridineRuII complexes 1a and 3a for photoinduced electron transfer have been synthesized and investigated. The complexes are synthesized in a convergent manner and are isolated as linear, single isomers. Time-resolved absorption spectroscopy reveals long-lived, photoinduced charge-separated states(tCSS (1a)=140 ns, tCSS (3a)=200 ns) formed by stepwise electron transfer.The overall yields of charge separation (Yield 50% for complex 1a and Yield 95% for complex 3a) are unprecedented for bis-tridentate RuII polypyridyl complexes.This is attributed to the longlived excited state of the [Ru(dqp)2]2+ complex combined with fast electron transfer from the donor moiety following the initial charge separation. The rodlike arrangement of donor and acceptor gives controlled, vectorial electron transfer, free from the complications of stereoisomeric diversity. Thus, such arrays provide an excellent system for the study of photoinduced electron transfer and, ultimately, the harvesting of solar energy.

Place, publisher, year, edition, pages
Weinhem: Wiley-VCH , 2010. Vol. 16, no 9, 2830-2842 p.
Keyword [en]
donor-acceptor systems, electron transfer, photochemistry, ruthenium, tridentate ligands
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-113609DOI: 10.1002/chem.200902716ISI: 000275943000024PubMedID: 20087914OAI: oai:DiVA.org:uu-113609DiVA: diva2:304936
Available from: 2010-03-22 Created: 2010-02-01 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Single and Accumulative Electron Transfer – Prerequisites for Artificial Photosynthesis
Open this publication in new window or tab >>Single and Accumulative Electron Transfer – Prerequisites for Artificial Photosynthesis
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Photoinduced electron transfer is involved in a number of photochemical and photobiological processes. One example of this is photosynthesis, where the absorption of sunlight leads to the formation of charge-separated states by electron transfer. The redox equivalents built up by successive photoabsorption and electron transfer is further used for the oxidation of water and reduction of carbon dioxide to sugars. The work presented in this thesis is part of an interdisciplinary effort aiming at a functional mimic of photosynthesis. The goal of this project is to utilize sunlight to produce renewable fuels from sun and water. Specifically, this thesis concerns photoinduced electron transfer in donor(D)-photosensitizer(P)-acceptor(A) systems, in mimic of the primary events of photosynthesis.

The absorption of a photon typically leads to transfer of a single electron, i.e., charge separation to produce a single electron-hole pair. This fundamental process was studied in several molecular systems. The purpose of these studies was optimization of single electron transfer as to obtain charge separation in high yields, with minimum losses to competing photoreactions such as energy transfer. Also, the lifetime of the charge separated state and the confinement of the electron and hole in three-dimensional space are important in practical applications. This led us to explore molecular motifs for linear arrays based on Ru(II)bis-tridentate and Ru(II)tris-bidentate complexes.

The target multi-electron catalytic reactions of water-splitting and fuel production require a build-up of redox equivalents upon successive photoexcitation and electron transfer events. The possibilities and challenges associated with such processes in molecular systems were investigated. One of the studied systems was shown to accumulate two electrons and two holes upon two successive excitations, without sacrificial redox agents and with minimum yield losses. From these studies, we have gained better understanding of the obstacles associated with step-wise photoaccumulation of charge and how to overcome them.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2010. 77 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 735
Keyword
Artificial photosynthesis, Photoinduced charge separation, Electron transfer, Energy transfer, Accumulative electon transfer, Donor-acceptor, Ruthenium, Linear arrays
National Category
Physical Chemistry
Research subject
Chemistry with specialization in Chemical Physics
Identifiers
urn:nbn:se:uu:diva-122206 (URN)978-91-554-7791-2 (ISBN)
Public defence
2010-05-21, Polhemsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
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Available from: 2010-04-28 Created: 2010-04-07 Last updated: 2011-03-01Bibliographically approved

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Karlsson, SusanneBergquist, Jonas

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