Electrochemistry of encapsulated guests: Ferrocene inside Cram's hemicarcerands

Sandra Mendoza, Pablo D. Davidov, Angel E. Kaifer

Research output: Contribution to journalArticle

56 Scopus citations

Abstract

The voltammetric behavior of ferrocene encapsulated inside two hemicarcerand hosts was investigated in dichloromethane and tetrachloroethane solutions. Molecular encapsulation led to substantial changes in the anodic voltammetric behavior of the ferrocene nucleus. Generally, encapsulated ferrocene exhibited a more positive half-wave oxidation potential and a lower apparent standard rate constant of heterogeneous electron transfer than uncomplexed ferrocene under identical experimental conditions. Whereas the anodic shift of the half-wave potential probably results from the hindered solvation of the positively charged, oxidized ferrocene inside the nonpolar hemicarcerand cavities, the observed decrease in electron transfer rate seems to arise primarily from the increased molecular mass of the electro-inactive species and the longer distance of maximum approach between the ferrocene center and the electrode surface which is imposed by the encapsulating host. Generally, electrochemical oxidation did not significantly alter the slow rate of ferrocene guest dissociation or release from the hemicarceplexes surveyed.

Original languageEnglish (US)
Pages (from-to)864-870
Number of pages7
JournalChemistry - A European Journal
Volume4
Issue number5
DOIs
StatePublished - Jan 1 1998

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Keywords

  • Electron transfer
  • Ferrocenes
  • Hemicarcerands
  • Host-guest chemistry
  • Molecular encapsulation
  • Sandwich complexes
  • Voltammetry

ASJC Scopus subject areas

  • Chemistry(all)

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