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RESEARCH PRODUCT

PI-Extension of porphyrins via intramolecular aromatic oxidative C-N coupling

subject

description

Π-extension of porphyrins has been performed via intramolecular oxidative C-N coupling of peripheral pyridinyl fragment(s) with the porphyrin core. These fusion reactions lead to the formation of C-N bond(s) between the substituent(s) and the porphyrin. The precursors were functionnalized with 2-mercaptopyridine, 8-hydoxyquinoline and 2-picoline at their meso or β-pyrrolic positions via aromatic nucleophlic substitution, cross-coupling reaction or reaction of the macrocycle with organolithium reagents. Voltametric analyses revealed some marked differences on the reactivity of the porphyrins depending on their substitution pattern and metalation (nickel(II) or zinc(II)). Chemical and electrochemical conditions were established to perform the intramolecular oxidative coupling and adapted depending on the substitution and metalation. The electrochemical, spectroscopic and structural properties of the fused products were analysed and compared to their respective precursors.