Synthesis and Photophysical Properties of 3,8-Disubstituted 1,10-Phenanthrolines and Their Ruthenium(II) Complexes

Authors

  • Michael Karnahl,

    1. Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, August-Bebel-Str. 2, 07743 Jena, Germany
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  • Sven Krieck,

    1. Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, August-Bebel-Str. 2, 07743 Jena, Germany
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  • Helmar Görls,

    1. Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, August-Bebel-Str. 2, 07743 Jena, Germany
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  • Stefanie Tschierlei,

    1. Institut für Physikalische Chemie, Friedrich-Schiller-Universität, Helmholzweg 4, 07743 Jena, Germany, Fax: +49-3641-948302
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  • Michael Schmitt,

    1. Institut für Physikalische Chemie, Friedrich-Schiller-Universität, Helmholzweg 4, 07743 Jena, Germany, Fax: +49-3641-948302
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  • Jürgen Popp,

    1. Institut für Physikalische Chemie, Friedrich-Schiller-Universität, Helmholzweg 4, 07743 Jena, Germany, Fax: +49-3641-948302
    2. Institute of Photonic Technology Jena e.V., Albert-Einstein-Straße 9, 07749 Jena, Germany
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    • Correspondence for Raman and resonance Raman spectra.

  • Daniel Chartrand,

    1. Département de Chimie, Université de Montréal, 2900 Edouard-Montpetit, Montréal, Québec H3T-1J4, Canada
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  • Garry S. Hanan,

    1. Département de Chimie, Université de Montréal, 2900 Edouard-Montpetit, Montréal, Québec H3T-1J4, Canada
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  • Robert Groarke,

    1. Solar Energy Conversion SRC, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland
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  • Johannes G. Vos,

    1. Solar Energy Conversion SRC, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland
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  • Sven Rau

    1. Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, August-Bebel-Str. 2, 07743 Jena, Germany
    2. Department for Chemistry and Pharmacy, Friedrich-Alexander-University Erlangen-Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany, Fax: +49-9131-8527367
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    • Correspondence for the synthesis and the materials.


Abstract

The palladium-catalysed cross-coupling reaction between 3,8-dibromo-1,10-phenanthroline with phenylacetylene or 3,5-bis(trifluoromethyl)phenylboronic acid gives good yields of the 3,8-disubstituted products. These 1,10-phenanthroline derivatives are used for the formation of novel ruthenium complexes of the type [(tbbpy)2Ru(phenR2)]2+ [where tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine, phen = 1,10-phenanthroline, R represents the substituents at the 3,8 positions with bromine, phenylacetylene or 3,5-bis(trifluoromethyl)phenyl]. All compounds are completely characterised by NMR and UV/Vis spectroscopy, MS, electrochemical measurements and Raman and resonance Raman spectroscopy. The photophysical properties indicate a strong influence of the substitution of the phenanthroline ligand on the absorption, emission and Raman properties. With resonance Raman spectroscopy the localisation of the singlet metal-to-ligand charge-transfer (1MLCT) excited state is determined. Thesolid-state structures of 3,8-dibromo-1,10-phenanthroline (phenBr2) and the corresponding ruthenium complex [(tbbpy)2Ru(phenBr2)]2+ and a structural motif of [(tbbpy)2Ru{phen-3,8-bis[3,5-bis(trifluoromethyl)phenyl]}]2+ are also reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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