A mechanism of the C₆₀ fullerene electropolymerization in the presence of dioxygen, O₂, in 0.1 M tetrabutylammonium perchlorate, in the toluene : acetonitrile (4 : 1, v : v) mixed solvent solution, was investigated by comparing mass spectrometric (MS) as well as simultaneous cyclic voltammetric (CV), electron spin resonance (ESR) and Vis-NIR spectroscopic behavior of products of both one- and two-electron reduction of C₆₀ in the absence and presence of O₂. For the first cathodic CV peak corresponding to the C₆₀/C₆₀^- electroreduction, the spectro-electrochemical behavior in the presence of O₂ was similar to that in its absence. That is, a Vis-NIR band at 1080 nm characteristic of C₆₀^- appeared if the potential was held at -0.445 V vs. Ag/Ag⁺ psuedo-reference electrode, i.e., at the first cathodic peak, indicating that C₆₀^- was electrogenerated. This anion did not chemically react with O₂ present in solution as there was only one strong MS peak with m/z of 720 characteristic of C₆₀ accompanied by weak peaks with m/z of 736 and 739 to 741 indicative of small amounts of C₆₀O and, presumably, C₆₀OH₄. Instead, an electron transfer from C₆₀^- to O₂ yielding superoxide, O₂^•-, was demonstrated by using in situ ESR spectroelectrochemistry combined with the spin-trap technique.

At more negative potentials, i.e., those at which C₆₀ is electroreduced to C₆₀^2- and O₂ to O₂^•-, the 1080-nm band vanished in the Vis-NIR spectrum and no new band emerged like if the electrogenerated C₆₀^2- was consumed in some following reaction resulting in a Vis-NIR inactive product. The ESR signal of the product with the g = 2.0007 value suggested the formation of some C₆₀ derivatives. Beside the main peak at m/z of 720 in the MS spectrum of the product, several additional peaks in the m/z range 739 to 760 appeared indicating that C₆₀O^•- and C₆₀O₂^•- were generated and, then, protonated. Moreover, several peaks in the m/z range 1297 to 1465 were observed. A peak with m/z of 1441.187 may indicate the formation of the [2 + 2] dimer, C₁₂₀. This peak is accompanied by a series of peaks corresponding to dimers, which last C_n (n = 1, 2) or C_2n (n = 2-5) carbon atoms. Apparently, C₆₀ can spontaneously dimerize after electroreduction of C₆₀ and O₂ to C₆₀^2- and O₂^•-, respectively. Importantly, no oxygen atom was built in the dimeric structure although superoxide radical promoted this dimerization.

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