Electrochemically Induced Dimerization of p 9 mp-C70(CF3)12 Trifluoromethylated Fullerene

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2021-09, Vol.125 (36), p.7876-7883
• Main Authors: Kosaya, Maria P, Yankova, Tatiana S, Rybalchenko, Alexey V, Tamm, Nadezhda B, Ioffe, Ilya N, Lukonina, Natalia S, Belov, Nikita M, Goryunkov, Alexey A
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.1c05656

We report a comprehensive study of a novel isomer of C70(CF3)12, p 9 mp-C70(CF3)12, whose electrochemical behavior differs from most of the other trifluoromethylated fullerenes. The addition pattern of p 9 mp-C70(CF3)12 is established by means of 19F–19F COSY NMR spectroscopy and DFT calculations. Like p 7 mp-C70(CF3)10, the new isomer p 9 mp-C70(CF3)12 undergoes dimerization to the [C70(CF3)12]2 2– upon single-electron reduction. The electrochemical observations are supported by the DFT calculations of dimerization energy and the temperature dependence of the CW X-band EPR spectroscopy data. Experimentally determined dimerization energies of p 9 mp-C70(CF3)12 –• and p 7 mp-C70(CF3)10 –• in solution are ca −8 and −26 kJ mol–1, respectively, in good correspondence with DFT data.