Syntheses and Optical and Electrochemical Properties of Porphyrin Dimers Linked by Metal Ions

Abstract

The preparation, isolation, and characterization of several new peripherally functionalized monomeric porphyrins and metalloporphyrins and of porphyrin dimers are described. These dimers are obtained by linking with metal ions two monomeric porphyrins bearing at their periphery an enaminoketone chelate fully conjugated with the aromatic ring. Porphyrin dimers linked by metal ions display large interactions in the ground state as evidenced by their electronic spectra and their electrochemical behavior. Compared to the monomeric analogue, these dimers show absorption spectra with intensified red-shifted Q-bands and their first oxidation potentials are substantially lowered and split into two distinct redox steps.

Synthesis, Characterization, and Electronic Properties of Metalloporphyrins Annulated to Exocyclic Imidazole and Imidazolium Rings

“…This reagent was previously used by Callot and co-workers to prepare porphyrins conjugated to enamino ketone and enamino aldehyde functions. [15] Complexes 11 and 12 were obtained in 82 and 90 % yield, respectively (Scheme 1).…”

Facile Formation of N‐Confused Porphyrin Dimers by Platinum(II) Coordination to the Outer‐Nitrogen Atoms

“…Such a strategy would be useful to build porphyrin arrays for the study of molecular wires, which are of current interest. [14] Received: January 22, 2003 [Z50995] .…”

Electrochemically Switchable Molecular-Tweezers

“…It is considered likely that the second redox wave of the other porphyrin appears at around 1.05 V and is thus buried in the base current. Richeter et al reported similar electrochemical behavior for a Ni-porphyrin dimer, which is closely bonded on planar through the metal complex 24 . On this basis we suggest that two redox waves based on Por/Por system result from the effect of the close intramolecular through-space interaction between the two porphyrins.…”