Synthesis of 4′-Functionalized 2,2′:6′,2′′-Terpyridines via the Pyridone Route: Symmetric and Asymmetric Bis-Complex Formation

Philip R. Andres; Harald Hofmeier; Bas G. G. Lohmeijer; Ulrich S. Schubert

doi:10.1055/s-2003-42443

PAPER

Synthesis of 4′-Functionalized 2,2′:6′,2′′-Terpyridines via the Pyridone Route: Symmetric and Asymmetric Bis-Complex Formation

Philip R. Andres^a,b, Harald Hofmeier^a,b, Bas G. G. Lohmeijer^a, Ulrich S. Schubert*^a,b
^a Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology and Dutch Polymer Institute, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
Fax: +31(40)2474186; e-Mail: u.s.schubert@tue.nl;
^b Center for NanoScience, Ludwig-Maximilians-Universität, Geschwister-Scholl Platz 1, 80333 München, Germany

Abstract

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Abstract

2,2′:6′,2′′-Terpyridines functionalized in the 4′-position have been prepared by reaction of 2,6-bis-(pyrid-2-yl)-4-pyridone under basic conditions with different electrophiles. The electrophiles consist of functionalized alkyl chains, which are terminated with different anionic leaving groups such as bromides, chlorides and tosylates. These reactions yielded terpyridines, which were modified at the 4′-position with heptoxy-, bromodecanoxy-, cyanopropoxy-, allyloxy-, styrene-4-ethoxy-, as well as (methoxyethoxy)-ethoxy functionalities. In an approach towards new functional materials based on polymerizable bis-terpyridyl metal-ion complexes, the 4′-epoxy-methoxy terpyridine was complexed with Co(II) in order to yield the paramagnetic bis-complex, which still could be characterized via ¹H NMR spectrometry. Additionally, in order to obtain an asymmetric bis-complex with two different terpyridine ligands, methyl-diethyleneoxy-terpyridine-Ru(II)-terpyridine-oxyheptane was prepared utilizing a directed coupling method via Ru(III)/Ru(II) chemistry.

Key words

terpyridines - metal complexes - epoxides - ruthenium - supramolecular chemistry

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