448218-67-5Relevant academic research and scientific papers
The redox properties of ferrocenyl-substituted aryl azines
Sauro, Vittorio A.,Workentin, Mark S.
, p. 250 - 262 (2002)
A series of ferrocenyl substituted azines (1-Fc/Ar, where Ar = 4-NO2C6H4, 4-CNC6H4, 4-OCH3C6H4, C5H4N, ferrocene, anthracene, and pyrene) were investigated by electrochemical and photochemical techniques. All the 1-Fc/Ar exhibited oxidation waves within 60 mV of each other, consistent with the expected oxidation of the ferrocene moiety. The reduction properties of 1-Fc/Ar is governed by the nature of the Ar substituent. The standard reduction potentials suggest that ferrocene has comparable electron donating abilities as a 4-methoxyphenyl and 4-dimethyl-aminophenyl group. The anthracenyl azines exhibit one-electron reversible reduction followed by dimerization of the radical anion resulting in dimerization rate constants (kd) between 5.1 × 104 and 1.5 × 105 M-1 s-1. 1-Fc/Anth and related azines undergo photochemical E/Z isomerization of the C=N bonds to produce E/Z and Z/Z isomers from the thermodynamically most stable E/E form. Fluorescence at 77 K, was observed for these compounds only after long-wavelength irradiation to produce a mixture of E/E, E/Z, and Z/Z isomers. Fluorescence quantum yields of 0.042, 0.090, and 0.176 were determined for 2-Anth/H, 2-Anth/Anth, and 1-Fc/Anth, respectively. The electrochemical, photochemical, and X-ray data suggest that the azine unit is a conjugation limiter and may be a general characteristic of azine molecules.
