Chemical and Electrochemical Dimerization of BODIPY Compounds: Electrogenerated Chemiluminescent Detection of Dimer Formation

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• 作者：Alexander B. Nepomnyashchii ; Martin Br枚ring ; Johannes Ahrens ; Allen J. Bard
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：December 7, 2011
• 年：2011
• 卷：133
• 期：48
• 页码：19498-19504
• 全文大小：941K
• 年卷期：v.133,no.48(December 7, 2011)
• ISSN：1520-5126

文摘

The electrochemistry of several difluoroboradiaza-s-indacene (BODIPY) compounds lacking substituent groups in the meso (8)- and/or 3 (伪)-positions was investigated. Chemical and electrochemical dimerization was demonstrated, and the dimerization depended on the character of substitution. The chemical dimerization was achieved by oxidative coupling using FeCl₃ in CH₂Cl₂ at 0 掳C. The electrochemical dimerization proceeded via anodic oxidation to the radical cation and monitored by both cyclic voltammetry (CV) and electrogenerated chemiluminescence (ECL). An available open 3-position was important for the formation of the dimer. The resulting 3,3鈥?dimer produced a second peak in the CV oxidation and also the appearance of a longer wavelength ECL peak at 656 nm, which is considerably shifted from the parent peak at 532 nm. No dimerization was seen for BODIPY molecules in which only the meso 8-position was unsubstituted, either by chemical or electrochemical means, demonstrating that dimerization occurs at position 3.