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Electrochemistry of nitride clusterfullerenes

In situ ESR spectroelectrochemistry of nitride clusterfullerenes

Another intriguing research focus of our group is the electrochemistry of fullerenes. We have systematically studied a series of clusterfullerene M3N@C80 (I) (M=Sc, Dy, Tm) to address the effect of the encaged cluster on their electrochemical behavior. Based on the comparison of the cyclic voltammograms of several tridysprosium Dy3N@C2n (n = 39, 40), i.e., Dy3N@C80 (I), Dy3N@C80 (II), and Dy3N@C78 (II), we revealed the effect of the symmetry and size of the fullerene cage on the electrochemical behavior of Dy3N@C2n (n = 39, 40). The fascinating finding of this study is that the Dy3N@C80 (I) monoanion exhibits a charge-induced reversible rearrangement of the structure, which may result from the change either of the Dy3N cluster (shape or position inside the cage) or of the cage symmetry (see next figure).

Electrochemistry of Dy3N@C80 (I)
CV_Dy3N@C80 (klick to enlarge)
Dy3N@C80 (I) in TBABF4/o-DCB with Ferrocene (Fc) as internal standard.
Inset: double-square reaction scheme.

In addition, in a recent finding we successfully probed the radical cation of Sc3N@C68 by in situ ESR/UV-Vis-NIR spectroelectrochemistry method, as shown in the next figure.


ESR spectrum of Sc3N@C68
ESR spectrum of the stable radical cation of the non-IPR Sc3N@C68 (D3:6140).

Contact

Prof. Lothar Dunsch

Address: IFW Dresden

Helmholtzstraße 20
01069 Dresden

Germany
Phone: +49 351 4659 660
Fax: +49 351 4659 811
Email: L.Dunsch@ifw-dresden.de