Electrochemical and Spectroelectrochemical Properties of Free‐Base Pyridyl‐ and N‐Alkyl‐4‐Pyridylporphyrins in Nonaqueous Media. Issue 1 (12th November 2015)

• Record Type: Journal Article
• Authors: Cui, Yan; Zeng, Lihan; Fang, Yuanyuan; Zhu, Jialiang; Xu, Hai‐Jun; Desbois, Nicolas; Gros, Claude P.; Kadish, Karl M.
• Is Part Of: ChemElectroChem. Volume 3:Issue 1(2016)
• Page Start: 110
• Page End: 121
• Publication Date: 2015-11-12
• Subjects: electrochemistry -- interacting centers -- nonaqueous media -- porphyrins -- spectroelectrochemistry; Electrochemistry -- Periodicals; 541.37
• DOI: 10.1002/celc.201500374
• Languages: English
• ISSNs: 2196-0216

Abstract

Abstract: Twelve structurally related pyridyl and meso ‐ N ‐methylpyridylporphyrin derivatives are investigated electrochemically in different nonaqueous media. The UV/Vis spectrum of each newly investigated porphyrin was measured before and after electroreduction and, based on this data, the site of electron transfer is proposed. An interaction occurs between the meso ‐pyridyl or meso ‐ N ‐alkyl‐4‐pyridyl substituents and the porphyrin π‐ring system, the magnitude of which depends upon the number of linked pyridyl or N ‐alkyl‐4‐pyridyl groups in the compound, the solvent, the supporting electrolyte, and/or other anions added to the solution. Abstract : All about that base : Twelve structurally related pyridyl and N ‐alkylpyridylporphyrin derivatives are examined as to their electrochemical and spectroelectrochemical properties in two nonaqueous media containing different supporting electrolytes. The electroactive N ‐alkylpyridyl groups in each compound can be sequentially reduced after a 2 e − addition to the conjugated macrocycle. Mono‐ N ‐methylpyridylporphyrin is proposed to involve a rearrangement of the double‐bonded structure for its doubly reduced form.