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Full Paper
Synthesis, Characterization, and Electrochemical Studies of New π-Extended Metalloporphyrins
Article first published online: 28 SEP 2009
DOI: 10.1002/ejoc.200900856
Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Jimenez, A. J., Jeandon, C., Gisselbrecht, J.-P. and Ruppert, R. (2009), Synthesis, Characterization, and Electrochemical Studies of New π-Extended Metalloporphyrins. European Journal of Organic Chemistry, 2009: 5725–5730. doi: 10.1002/ejoc.200900856
Publication History
- Issue published online: 3 NOV 2009
- Article first published online: 28 SEP 2009
- Manuscript Received: 28 JUL 2009
Funded by
- European Student Exchange Program (ERASMUS)
Keywords:
- Porphyrinoids;
- Oxidation;
- Cyclic voltammetry;
- Conjugation
Graphical Abstract
Doubly fused metalloporphyrins have been obtained in a few simple steps and the electronic properties of these new compounds studied by electrochemistry. The X-ray structure of the free base is reported.
Abstract
A doubly fused porphyrin has been synthesized by two successive cyclization reactions. The first meso-phenyl group was fused by an intramolecular Cadogan reaction leading to an enamine-functionalized porphyrin. After Vilsmeier–Haack formylation of the nickel enaminoporphyrin, an intramolecular Friedel–Crafts reaction followed by dehydration of the intermediate alcohol afforded the doubly fused aromatic nickel porphyrin, which could be demetalated. The free base and the copper and palladium porphyrins show extremely high absorbances in the 700–800 nm range. The palladium complex was a good catalyst for the oxidation of cholesterol with singlet oxygen, which makes this chromophore a potential candidate for photodynamic therapy.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)