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

•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...

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Published in:Electrochimica acta 2016-02, Vol.191, p.980-986
Main 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.
Format: Article
Language:English
Subjects:
cyclic voltammetry
DFT calculations
electrochemically promoted switching
methylenated fullerene
skeletal transformation
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Summary:•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 Cs-C70(CF3)8 was elaborated.•More compact alternatives promising molecular switching capabilities can be found within the family of pyramidalized polyenes. Despite trifluoromethylfullerene Cs-C70(CF3)8 has a multitude of available reaction sites, [2+1] cycloaddition of CX2 moieties (X=F and p-MeOC6H4) 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 0.6eV 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.
ISSN:0013-4686
1873-3859
DOI:10.1016/j.electacta.2016.01.125