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Synthesis 2012; 44(14): 2287-2294
DOI: 10.1055/s-0031-1289771
paper
© Georg Thieme Verlag Stuttgart · New York

Chelating Fluorene Dyes as Mono- and Ditopic 2-(1H-1,2,3-Triazol-4-yl)pyridine Ligands and Their Corresponding Ruthenium(II) Complexes

Bobby Happ
a   Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University of Jena, Humboldtstr. 10, 07743 Jena, Germany , Fax: +49(3641)948202   Email: ulrich.schubert@uni-jena.de
b   Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany
c   Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands
,
Johann Schäfer
b   Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany
d   Institute of Photonic Technology Jena (IPHT), Albert-Einstein-Str. 9, 07745 Jena, Germany
,
Christian Friebe
a   Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University of Jena, Humboldtstr. 10, 07743 Jena, Germany , Fax: +49(3641)948202   Email: ulrich.schubert@uni-jena.de
b   Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany
,
Helmar Görls
e   Laboratory of Inorganic and Analytical Chemistry, Friedrich Schiller University of Jena, Lessingstr. 8, 07743 Jena, Germany
,
Andreas Winter
a   Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University of Jena, Humboldtstr. 10, 07743 Jena, Germany , Fax: +49(3641)948202   Email: ulrich.schubert@uni-jena.de
b   Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany
c   Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands
,
Martin D. Hager
a   Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University of Jena, Humboldtstr. 10, 07743 Jena, Germany , Fax: +49(3641)948202   Email: ulrich.schubert@uni-jena.de
b   Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany
c   Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands
,
Jürgen Popp
b   Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany
d   Institute of Photonic Technology Jena (IPHT), Albert-Einstein-Str. 9, 07745 Jena, Germany
f   Institute for Physical Chemistry (IPC) and Abbe Center of Photonics (ACP), Friedrich Schiller University of Jena, Helmholtzweg 4, 07743 Jena, Germany
,
Benjamin Dietzek
b   Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany
d   Institute of Photonic Technology Jena (IPHT), Albert-Einstein-Str. 9, 07745 Jena, Germany
f   Institute for Physical Chemistry (IPC) and Abbe Center of Photonics (ACP), Friedrich Schiller University of Jena, Helmholtzweg 4, 07743 Jena, Germany
,
Ulrich S. Schubert*
a   Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University of Jena, Humboldtstr. 10, 07743 Jena, Germany , Fax: +49(3641)948202   Email: ulrich.schubert@uni-jena.de
b   Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstraße 10, 07743 Jena, Germany
c   Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands
› Author Affiliations
Further Information

Publication History

Received: 09 January 2012

Accepted after revision: 28 April 2012

Publication Date:
18 June 2012 (online)

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Abstract

2-(1H-1,2,3-Triazol-4-yl)pyridines (trzpy), which can be regarded as analogues to 2,2′-bipyridines, were attached to the 2- and 7-position of 9,9-dioctyl-9H-fluorene providing one monotopic and two ditopic ligands. The bidentate N-heterocycles were synthesized by the copper(I)-catalyzed azide-alkyne 1,3-cycloaddition. Moreover, the palladium(0)-catalyzed Sonogashira coupling allowed the introduction of an electron-withdrawing phenylacetylene moiety at 5-position of the pyridine unit. The emission maximum of the ligands could be varied over a range of 100 nm with extinction coefficients up to 95 000 M–1·cm–1. Even though the monotopic system revealed a similar absorption behavior compared to its ditopic counterpart, a remarkable fluorescence quantum yield deviation of one order of magnitude was observed (Φ = 0.66 for the unsubstituted ditopic and Φ = 0.07 for the monotopic ligand). All trzpy systems were coordinated to ruthenium(II) ions in high yields (>90%) using the bis(4,4′-dimethyl-2,2′-bipyridine)ruthenium(II) precursor. Though 2-(1,2,3-triazol-4-yl)pyridine ligands are known to be potential quenchers for ruthenium(II) ions, all ruthenium complexes revealed room temperature phosphorescence, whereby emission lifetimes proved to be relatively short (<10 ns). Photophysical and electrochemical measurements indicated no electronic interaction of the two ruthenium centers.

Key words

copper(I)-catalyzed azide-alkyne cycloaddition - CuAAC reaction - fluorine - photophysics - ruthenium - phosphorescence

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis. Included are 1H NMR and 13C NMR spectra for 3, 6, 9–12, cyclic voltammograms of 10 and 11, lifetime measurements and photoluminescence spectra at 77 K for 10–12.
  • Supporting Information
 

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