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

• Published in: Journal of the American Chemical Society Vol. 124; no. 21; pp. 6168 - 6179
• Main Authors: Richeter, Sébastien, Jeandon, Christophe, Gisselbrecht, Jean-Paul, Ruppert, Romain, Callot, Henry J
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 29.05.2002; Amer Chemical Soc
• Subjects: Amination; Cations - chemistry; Chemistry; Chemistry, Multidisciplinary; Coordination compounds; Crystallography, X-Ray; Electrochemistry; Exact sciences and technology; Inorganic chemistry and origins of life; Ketones - chemistry; Metalloporphyrins - chemical synthesis; Metalloporphyrins - chemistry; Metals - chemistry; Oxidation-Reduction; Physical Sciences; Preparations and properties; Science & Technology; Spectrophotometry, Ultraviolet; VICARIOUS NUCLEOPHILIC AMINATION; ELECTRON-TRANSFER; MOLECULAR WIRES; BUILDING-BLOCKS; PHOTOINDUCED ENERGY; MULTIPORPHYRIN ARRAYS; PI-SYSTEMS; TEMPLATE-DIRECTED SYNTHESIS; PHOTOPHYSICAL PROPERTIES; FUSED OLIGOPORPHYRINS; Electrochemical potential; Nickel Complexes; Nitrogen heterocycle; Palladium Complexes; Organic ligand; NMR spectrometry; Transition metal Complexes; Cyclic voltammetry; Electrochemical properties; Optical properties; Platinoid Complexes; Metalloporphyrin; Dimerization; Ultraviolet visible spectrometry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja017531n

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.