Abstract
The electrochemistry of three new clusterfullerenes Dy~3~N@C~2__n__~ (2__n__=78, 80), namely two isomers of Dy~3~N@C~80~ (I and II) as well as Dy~3~N@C~78~ (II), have been studied systematically including their redox‐reaction mechanism. The cyclic voltammogram of Dy~3~N@C~80~ (I) (I~h~) exhibits two electrochemically irreversible but chemically reversible reduction steps and one reversible oxidation step. Such a redox pattern is quite different from that of Sc~3~N@C~80~ (I), and this can be understood by considering the difference in the charge transfer from the encaged cluster to the cage. A double‐square reaction scheme is proposed to explain the observed redox‐reaction behavior, which involves the charge‐induced reversible rearrangement of the Dy~3~N@C~80~ (I) monoanion. The first oxidation potential of Dy~3~N@C~80~ (II) (D~5__h__~) has a negative shift of 290 mV relative to that of Dy~3~N@C~80~ (I) (I~h~), indicating that lowering the molecular symmetry of the clusterfullerene cage results in a prominent increase in the electron‐donating property. The first and second reduction potentials of Dy~3~N@C~78~ (II) are negatively shifted relative to those of Dy~3~N@C~80~ (I, II), pointing to the former's lowered electron‐accepting ability. The significant difference in the electrochemical energy gaps of Dy~3~N@C~80~ (I), Dy~3~N@C~80~ (II), and Dy~3~N@C~78~ (II) is consistent with the difference in their optical energy gaps.