Optical electron transfer processes. The dependence of intervalence line shape and transition energy on chromophore concentration

Robert L. Blackbourn*, Joseph T. Hupp

*Corresponding author for this work

Research output: Contribution to journalArticle

35 Scopus citations

Abstract

Optical electron transfer in the mixed-valence cation of biferrocenylacetylene (BF+) has been examined in CD2Cl2 solvent. The intervalence absorption line shape is relatively narrow at both low and high chromophore concentrations, but broader at intermediate concentrations. The transition energy for metal-to-metal charge transfer increases from ≈4440 cm-1 at infinite dilution to 5995 cm-1 for 3.8 mM BF+. Related effects exist due to added electrolyte. Neither the electrolyte nor chromophore concentration effects are expected from a simple reading of electron transfer theories. Nevertheless, both phenomena can be understood and within the context of theory upon careful consideration of the effects of ion-pairing (and tripling) equilibria upon electron-transfer energetics.

Original languageEnglish (US)
Pages (from-to)399-405
Number of pages7
JournalChemical Physics Letters
Volume150
Issue number6
DOIs
StatePublished - Sep 23 1988

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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