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Facile synthesis of bistridentate Ru(II) complexes based on 2,6-di(quinolin-8-yl)pyridyl ligands: sensitizers with microsecond 3MLCT excited state lifetimes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
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2009 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 48, no 7, 3228-3238 p.Article in journal (Refereed) Published
Abstract [en]

Synthetic routes to meridional bistridentate ruthenium(II) complexes based on 2,6-di(quinolin-8-yl)pyridyl (dqp) ligands have been investigated. Microwave-assisted synthesis at 200 degrees C allowed the high yield (49-87%) preparation of homoleptic meridional [Ru(dqp)(2)](2+)-based complexes containing inert functional groups. Applying this protocol for the synthesis of mer-[Ru(dqp)(2)](2+) (mer-1) but lowering the temperature to 180 degrees C and shorter reaction times revealed the formation of the facial isomers cis,fac-1 and trans,fac-1 (56% and 12% yields, respectively). The facial isomers were characterized by NMR spectroscopy and X-ray diffraction analysis. In a stepwise protocol, the reaction of Ru(dqp)Cl(3) or Ru(dqp)(L)Cl(2) (L = MeCN or DMSO) and a second equivalent dqp gave mer-1 in 12-26% yields and N(5)Cl-coordinated [Ru(dqp)(2)Cl](+) (28-46%). [Ru(dqp(2))Cl](+) was photochemically, or thermally in the presence of Ag(I), converted to mer-1. By using mer-[Ru(dqp)(MeCN)(3)] (2+), which was crystallographically characterized, a wide range of homo- and heteroleptic meridional [Ru(dqp)(2)](2+)-based complexes was synthesized in up to 77% yield. The synthetic utility of meridional [Ru(dqp)(2)](2+)-based complexes as building blocks was demonstrated by palladium-catalyzed homocoupling of mer-[Ru(dqp)(dqpPhBr)](2+) to form a dinuclear complex. The redox and photophysical properties of the meridional complexes are discussed.

Place, publisher, year, edition, pages
2009. Vol. 48, no 7, 3228-3238 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-98074DOI: 10.1021/ic802342tISI: 000264759500062PubMedID: 19254036OAI: oai:DiVA.org:uu-98074DiVA: diva2:173245
Available from: 2009-02-04 Created: 2009-02-04 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Beyond Classical Ruthenium(II) Polypyridyl Complexes: Photosensitizers as Building Blocks For Linear Donor-Photosensitizer-Acceptor Assemblies
Open this publication in new window or tab >>Beyond Classical Ruthenium(II) Polypyridyl Complexes: Photosensitizers as Building Blocks For Linear Donor-Photosensitizer-Acceptor Assemblies
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes ruthenium(II) polypyridyl-type complexes tailored for artificial photosynthesis. Inspired by Nature, the primary events in photosystem II are mimicked by donor-photosensitizer-acceptor (D-P-A) assemblies. The photosensitizer plays a key role in such processes, and the combination of structural and photophysical properties is essential to control the electron transfer steps. In the first part, the general requirements for photosensitizers are discussed.

The second part deals with [Ru(bpy)3]2+-benzoquinone (Q) dyads (bpy is 2,2´-bipyridine) based on an asymmetric 5,5´-bisamide substituted bpy. Rapid electron-transfer from the excited state is observed to generate the RuIII-Q- charge separated states but preliminary results show no effect of the directionality of the amide link.

In the main part, a strategy to overcome the photophysical limitations of RuII bistridentate complexes (e.g. [Ru(tpy)2]2+, tpy is 2,2´:6´,2´´-terpyridine) is explored. The prototypical [Ru(dqp)2]2+ complex (dqp is 2,6-di(quinolin-8-yl)pyridine) is synthesized which displays a 3000 ns excited state lifetime at room temperature, reversible redox chemistry and high photostability. The synthesis of 4-substituted dqp is achieved via SUZUKI coupling using 8-quinoline boronic acid or ring-formation of the central pyridine. A markedly rich Ru coordination chemistry was observed, e.g. facial and meridional isomers of [Ru(dqp)2]2+. Using a chloride-free [Ru(dqp-R)(MeCN)3]2+ intermediate allows the synthesis of heteroleptic meridional [Ru(dqp-R)(dqp-R’)]2+ (R,R’ = -H, -CO2Et, -NH2, -OMe, -Br, -PhBr, …) in high yields. The meridional complexes show long-lived luminescence (450 - 5500 ns) and reversible redox chemistry. The photochemical reactivity has been investigated in typical electron-transfer reactions, e.g. in a supramolecular P-A dyad and in a multimolecular approach using biomimetic components (Mn and Fe complexes).

The dqp ligand is further used to synthesize FeII, RhIII, cyclometallating RuII complexes and an aza-analogue of [Ru(dqp)2]2+ and is discussed in the final part. These complexes were prepared with the aim to further tune the redox properties while maintaining good photophysical properties.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2009. 58 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 602
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-9555 (URN)978-91-554-7408-9 (ISBN)
Public defence
2009-03-20, Häggsalen, Ångström Laboratories, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2009-02-26 Created: 2009-02-04 Last updated: 2011-06-10Bibliographically approved

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