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Charge‐Induced Reversible Rearrangement of Endohedral Fullerenes: Electrochemistry of Tridysprosium Nitride Clusterfullerenes Dy 3 N@C 2 n (2 n =78, 80)
Author(s) -
Yang Shangfeng,
Zalibera Michal,
Rapta Peter,
Dunsch Lothar
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200501578
Subject(s) - redox , electrochemistry , chemistry , crystallography , endohedral fullerene , electron transfer , fullerene , inorganic chemistry , electrode , organic chemistry
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.