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DOI: 10.1055/s-0031-1289771
Chelating Fluorene Dyes as Mono- and Ditopic 2-(1H-1,2,3-Triazol-4-yl)pyridine Ligands and Their Corresponding Ruthenium(II) Complexes
Publikationsverlauf
Received: 09. Januar 2012
Accepted after revision: 28. April 2012
Publikationsdatum:
18. Juni 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 - phosphorescenceSupporting 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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