Optimizing Electron Transfer Mediators Based on Arylimidazoles by Ring Fusion: Synthesis, Electrochemistry, and Computational Analysis of 2-Aryl-1-methylphenanthro[9,10-d]imidazoles

• Published in: Journal of the American Chemical Society Vol. 136; no. 1; pp. 427 - 435
• Main Authors: Francke, Robert, Little, R. Daniel
• Format: Journal Article
• Language: English
• Published: WASHINGTON Amer Chemical Soc 08.01.2014
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; CATION RADICALS; ENERGY; REDOX CATALYSTS; REARRANGEMENTS; CONVERSION; ANODIC-OXIDATION
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja410865z

A significant improvement of the properties of redox catalysts based on the triarylimidazole framework can be achieved with a simple structural modification. By linking the ortho-carbons of the aromatics positioned at C-4 and C-5, a fused framework is generated, removing the distortion from planarity and enhancing the influence of the substituents on the redox properties. This modification leads not only to a much broader range of available redox potentials for the resulting phenanthro[9,10-d]imidazoles but also to improved stability of the corresponding radical cation. These concepts were verified with eight new phenanthro[9,10-d]imidazole derivatives, using cyclic voltammetry and DFT calculations. For this purpose, an optimized and general synthetic route to the desired compounds was developed. An excellent linear correlation of the calculated effective ionization potentials with the experimental oxidation potentials was obtained, allowing for an accurate prediction of oxidation potentials of derivatives yet to be synthesized. Moreover, high catalytic activity was found for electro-oxidative C-H activation reactions.