Abstract
Reduction potential (Ered) values have been calculated and compared with available cyclic voltammetry (CV) data for 10 metallofullerene complexes with the μ3-η2:η2: η2-C60 (M3-C6[C60]) bonding mode. Consideration of bulk solvent effects is essential for the calculation of the Ered values. Scaling factors for the electrostatic terms of the solvation energies have been introduced to fully describe the experimental cyclic voltammograms with a small mean deviation of 0.07 V. Multiple electron reductions induce movement of the metal cluster moieties on the C60 surface, which is accompanied with the changes in some M-C[C60] bonds from π-type to σ-type mode, However, the changes in M3-C60 distances, as well as the geometric changes of M3 and C60, are small for the reductions, which is in harmony with the high chemical and electrochemical stability of the metallofullerenes. Our population analyses reveal that the added electrons are not localized at the C60 moieties, and electron population in the metal clusters is significant, more than 20% (av. 37%), for all the reductions. Furthermore, we demonstrated that the two close one-electron redox waves in CV diagrams are strongly correlated with significant electron delocalization, about 40-80%, to the metal-cluster moieties in these metallofullerene complexes.
Original language | English |
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Pages (from-to) | 1100-1106 |
Number of pages | 7 |
Journal | Journal of Computational Chemistry |
Volume | 28 |
Issue number | 6 |
DOIs | |
State | Published - 30 Apr 2007 |
Keywords
- Cyclic voltammetry
- Density functional theory
- Electron delocalization
- Metallofullerene
- Reduction potential