Electron affinities of [5, 6]-open and [5, 6]-closed adducts of trifluoromethylfullerene Cs-C70(CF3)8: even one bond matters!. (10th February 2016)

• Record Type: Journal Article
• Authors: Rybalchenko, Alexey V.; Apenova, Marina G.; Semivrazhskaya, Olesya O.; Belov, Nikita M.; Markov, Vitaliy Yu.; Troyanov, Sergey I.; Ioffe, Ilya N.; Lukonina, Natalia S.; Sidorov, Lev N.; Magdesieva, Tatiana V.; Goryunkov, Alexey A.
• Is Part Of: Electrochimica acta. Volume 191(2016)
• Page Start: 980
• Page End: 986
• Publication Date: 2016-02-10
• Subjects: methylenated fullerene -- electrochemically promoted switching -- cyclic voltammetry -- DFT calculations -- skeletal transformation; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2016.01.125
• Languages: English
• ISSNs: 0013-4686

Abstract

Highlights: Crucial influence of open-closed skeletal transitions on the electronic properties of fullerene was demonstrated. Electrochemically promoted switching of electronic properties based on disruption of the conjugated 62π-electron system into the isolated 32 and 28π-electron fragments upon closing the [5, 6]-bond in question. Regioselective near-equatorial cycloproponation of trifluoromethylfullerene C s -C70 (CF3 )8 was elaborated. More compact alternatives promising molecular switching capabilities can be found within the family of pyramidalized polyenes. Abstract: Despite trifluoromethylfullerene C s -C70 (CF3 )8 has a multitude of available reaction sites, [2 + 1] cycloaddition of CX2 moieties (X = F and p -MeOC6 H4 ) proceeds regioselectively at a particular [5, 6]-bond. Depending on the nature of X, the resulting derivative can be either [5, 6]-open (i.e., the said CC bond is cleaved) or [5, 6]-closed, and this structural detail, seemingly insignificant for a molecule that large, brings about a remarkable 0.6 eV difference in the electron affinity, as revealed by electrochemical studies. Synthesis, structural and electrochemical elucidation of the C70 (CF3 )8 (CX2 ) compounds are discussed, as well as electrochemically promoted switching of the electronic properties based on disruption of the conjugated 62π-electron system into the isolated 32 and 28π-electron fragments upon closing the [5, 6]-bond.