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Subject: Spectroelectrochemistry × WGL Institute: IFWD ×

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    An in situ spectroelectrochemical study of the dimeric phthalocyanines [(SiPc)2O][OSiHx3]2, [(SiPc)2O][OSiHx3]2radical dot+, and [(SiPc)2O][OSiHx3]22+
    (2021) Dmitrieva, Evgenia; Sturtz, Benjamin W.; Yang, Yang; Zhang, Ping; Dunsch, Lothar; Kenney, Malcolm E.
    An in situ spectroelectrochemical study of the oxidation of the μ-oxosilicon phthalocyanine dimer [(SiPc)2O][OSiHx3]2 utilizing cyclic voltammetry, electron spin resonance spectroscopy, and visible–near infrared spectroscopy has been carried out. The results of this study show that oxidation of the dimer yields the paramagnetic radical dimer [(SiPc)2O][OSiHx3]2radical dot+ and then the diamagnetic dimer [(SiPc)2O][OSiHx3]22+. The study shows that the rings of [(SiPc)2O][OSiHx3]22+ are antiferromagnetically coupled.
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    Electron-transfer initiated nucleophilic substitution of thiophenolate anion by 1-chloro-substituted 4-(thiazol-2-ylazo)naphthalenes
    (Amsterdam : Elsevier B.V., 2020) Dmitrieva, E.; Yu, X.; Hartmann, H.
    In this work, the electrochemical transformation of 5-chloro-2-[(4-chloronaphthalen-1-yl)azo]thiazoles (A) into the corresponding radical anion A·− and its subsequent reaction with diphenyldisulfide (PhSSPh) was studied. It was found that the primarily generated azo anion radical A·− is able to initiate an electron transfer process which converts the disulfide into its thiolate anion PhS−. This anion was subsequently able to substitute the Cl- and H-groups by phenylmercapto moieties in the starting azo compound A. The structures of the phenylmercapto-substituted azo compounds thus generated were confirmed by thin-layer chromatography and mass spectrometry using independently prepared compounds as references.