Cyclic voltammetry modeling, geometries, and electronic properties for metallofullerene complexes with μ32: η22-C60 bonding mode

Kyoung Hoon Kim, Jaehoon Jung, Bo Keun Park, Young Kyu Han, Joon T. Park

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Reduction potential (Ered) values have been calculated and compared with available cyclic voltammetry (CV) data for 10 metallofullerene complexes with the μ322: 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 languageEnglish
Pages (from-to)1100-1106
Number of pages7
JournalJournal of Computational Chemistry
Volume28
Issue number6
DOIs
StatePublished - 30 Apr 2007

Keywords

  • Cyclic voltammetry
  • Density functional theory
  • Electron delocalization
  • Metallofullerene
  • Reduction potential

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