1026495-65-7Relevant academic research and scientific papers
Stable Thioaminyl Radicals Having Functional Groups: Generation, ESR Spectra, Isolation, X-ray Crystallographic Analyses, and Magnetic Characterization of N-(Arylthio)-4-(ethoxycarbonyl)-2,6-diarylphenylaminyls, N-(Arylthio)-4-acetyl-2,6-diarylphenylaminyls, and N-(Arylthio)-4-cyano-2,6-diarylphenylaminyls
Miura, Yozo,Momoki, Masayoshi,Nakatsuji, Masaaki,Teki, Yoshio
, p. 1555 - 1565 (2007/10/03)
Oxidation of N-(arylthio)-4-(ethoxycarbonyl)-2,6-diarylanilines (9), N-(arylthio)-4-acetyl-2,6-diarylanilines (10), and N-(arylthio)-4-cyano-2,6-diarylanilines (11) with PbO2 yielded quite persistent N-(arylthio)-4-(ethoxycarbonyl)-2,6-diarylphenylaminyls(4), N-(arylthio)-4-acetyl-2,6-diarylphenylaminyls (5), and N-(arylthio)-4-cyano-2,6-diarylphenylaminyls (6), respectively, and they were isolated as pure radical crystals. On the other hand, N-(arylthio)-4-nitro-2,6-diarylphenylaminyls (6), and N-(arylthio)-4-chloro-2,6-diarylphenylaminyls (7), were unstable and soon decomposed. The X-ray crystallographic analyses of N-[(2,4-dichlorophenyl)thio]-4-acetyl-2,6-diphenylphenylaminyl (5c) and N-[(2,4-dichlorophenyl)thio]-4-cyano-2,6-diphenylphenylaminyl (6c) showed that the Ph-N-S-Ph π-framework is planar, and the 2- and 6-phenyl groups are twisted from the coplane. The ESR studies for 4-8 showed that their hyperfine coupling constants are nearly identical to each other and that the unpaired electron is extensively delocalized onto the anilino benzene ring and the arylthiyl group. The magnetic susceptibility measurements were carried out for five thioaminyl radical crystals and showed that one radical couples ferromagnetically with 2J/kB = 16.0 K, and the other four radicals couple antiferromagnetically with 2J/kB = -15.6 to -194.6 K or θ = -0.6 to -5.0 K.
