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Issue 28, 2010
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An endohedral redox system in a fullerene cage: the Ce based mixed-metal clusterfullerene Lu2CeN@C80

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Abstract

Redox reactions of endohedral fullerenes, and especially their oxidation, usually result in a change of the redox state of the carbon cage. Here we demonstrate that an oxidation of the endohedral species is possible bypassing the fullerene cage in an unprecedented reversible cascade electron transfer under anodic conditions. The first Ce-based non-scandium mixed-metal nitride clusterfullerene (NCF) Lu2CeN@C80(Ih) was synthesized and isolated. The electronic and vibrational properties of Lu2CeN@C80 are characterized by UV-vis-NIR and FTIR spectroscopies and the cage structure of Lu2CeN@C80 is determined by 13C NMR spectroscopy to be C80(Ih). At room temperature the NMR peak positions are shifted from the normal values of the diamagnetic M3N@C80 NCFs because of the unpaired f-electron localized on the Ce atom in the Ce3+ state. The variable-temperature NMR study enabled the estimation of the diamagnetic terms in the 13C chemical shifts, which were found to be close to those of diamagnetic M3N@C80 NCFs. The electrochemical properties of Lu2CeN@C80 were investigated by cyclic and square wave voltammetry, revealing two electrochemically irreversible but chemically reversible reduction steps and one reversible oxidation step. As the oxidation potential is significantly less positive than that in all other M3N@C80 NCFs, we conclude that an oxidation of the endohedral Ce occurs with the formation of Lu2CeIVN@C80+, the first endohedral metallofullerene species with the tetra-valent cerium atom. This hypothesis is also supported by DFT calculations.

Graphical abstract: An endohedral redox system in a fullerene cage: the Ce based mixed-metal cluster fullerene Lu2CeN@C80

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Publication details

The article was received on 10 Feb 2010, accepted on 15 Apr 2010 and first published on 08 Jun 2010


Article type: Paper
DOI: 10.1039/C002918A
Phys. Chem. Chem. Phys., 2010,12, 7840-7847

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    An endohedral redox system in a fullerene cage: the Ce based mixed-metal cluster fullerene Lu2CeN@C80

    L. Zhang, A. A. Popov, S. Yang, S. Klod, P. Rapta and L. Dunsch, Phys. Chem. Chem. Phys., 2010, 12, 7840
    DOI: 10.1039/C002918A

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