Mechanistic studies of the electrochemical polymerization of C60 in the presence of dioxygen or C60O

Elena P. Krinichnaya; Alexander P. Moravsky; Oleg Efimov; Janusz W. Sobczak; Krzysztof Winkler; Wlodzimierz Kutner; Alan L. Balch

doi:10.1039/B416357E

Mechanistic studies of the electrochemical polymerization of C₆₀ in the presence of dioxygen or C₆₀O†

Elena P. Krinichnaya,^a Alexander P. Moravsky,‡^a Oleg Efimov,^a Janusz W. Sobczak,^b Krzysztof Winkler,*^cd Wlodzimierz Kutner*^be and Alan L. Balch*^d

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* Corresponding authors

^a Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 142432 Moscow Region, Institutsky Str. 18, Russia

^b Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

^c Institute of Chemistry, University of Bialystok, Al. J. Pilsudskiego 11/4, 15443 Bialystok, Poland
E-mail: winkler@uwb.edu.pl

^d Department of Chemistry, University of California, Davis, California 95616, USA
E-mail: albalch@ucdavis.edu

^e Cardinal Stefan Wyszynski University in Warsaw, Faculty of Mathematics and Natural Sciences, School of Science, Dewajtis, 01-815 Warsaw, Poland
E-mail: wkutner@ichf.edu.pl

Abstract

Electropolymerization of C₆₀ in the presence of dioxygen, in a mixture of acetonitrile and toluene (1 : 4, v : v) containing tetra(alkyl)ammonium perchlorate, was investigated by multi-scan cyclic voltammetry and piezoelectric microgravimetry with the use of an electrochemical quartz crystal microbalance. The fullerene was readily electropolymerized if the O₂ to C₆₀ concentration ratio in solution exceeded 1 : 10 and the applied potential reached values where electro-reduction of dioxygen to superoxide, O₂˙⁻, and C₆₀ to C₆₀²⁻ occurred. The redox activity of the polymer was determined by cyclic voltammetry for solutions with different tetra-(alkyl)ammonium perchlorates used as supporting electrolytes. The film conductivity was higher the smaller the size of the cation in the supporting electrolyte. The C₆₀ electropolymerization in the presence of dioxygen was suppressed when a spin trapping agent, N-tert-butyl-α-(4-nitrophenyl)nitrone that could intercept superoxide, was present. The fullerene was also electropolymerized in the presence of small amounts of the epoxide, C₆₀O, in the absence of dioxygen. We postulate that the C₆₀ electropolymerization in the presence of O₂ proceeds via the initial nucleophilic attack of superoxide on C₆₀ to form a C₆₀O₂˙⁻ radical anion, which then interacts with another molecule of C₆₀ to produce C₆₀O and C₆₀O˙⁻. Under further electro-reduction, these intermediates serve to initiate polymerization of C₆₀ through the formation of C₆₀O²⁻, as determined earlier in studies of the electropolymerization of C₆₀O itself.

Journal of Materials Chemistry

Mechanistic studies of the electrochemical polymerization of C₆₀ in the presence of dioxygen or C₆₀O†

Abstract

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Mechanistic studies of the electrochemical polymerization of C₆₀ in the presence of dioxygen or C₆₀O

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Journal of Materials Chemistry