Making connections between metallofullerenes and fullerenes: electrochemical investigations Original Research Article

The square-wave voltammetry for a series of related fullerenes and metallofullerenes measured in pyridine solutions containing 0.10 M tetra-n-butylammonium perchlorate is reported. Several dimetallic metallofullerenes, M2@Cx (where M=Sc or Er, and x=82 or 84), are found to have similar voltammetric responses regardless of metal identity or carbon number. Assignment of formal charges to the fullerene cage suggests that these metallofullerenes are isoelectronic and have related molecular orbital structures. The voltammetry of the empty C82 and D2d-C84 cages are also alike, but are different from the square-wave voltammetry of the C60, C70, and D2-C84. The similarity of the voltammetry for C82 and D2d-C84, and for the C82 and C84 metallofullerenes is consistent with a related electronic structure for these species. There, however, is no clear correspondence between the voltammetry of the metallofullerenes and their corresponding empty cage fullerene.