The effects of electronic coupling and solvent broadening on the intervalent electron transfer of a centrosymmetric mixed-valence complex

David F. Watson, Andrew Bruce Bocarsly

Research output: Contribution to journalReview articlepeer-review

12 Scopus citations

Abstract

A three-dimensional nuclear coordinate representation of the intervalent electron transfer processes occurring in the trinuclear mixed-valence complex, [(NC)5Fe(II)-CN-Pt(IV)(NH3)4-NC-Fe(II)(CN) 5]4-, is discussed in terms of the degree of coupling between electronic states. The related dinuclear complex, (NC)5Fe(II)-CN-Pt(IV)-(NH3)5, has been synthesized and characterized by UV-vis and IR absorption spectroscopies, cyclic voltammetry, resonance Raman spectroscopy, and single crystal X-ray diffraction. The visible absorption spectra and time-dependent resonance Raman intensity analyses of the two complexes are compared with regard to the amount of electronic coupling in the trinuclear complex. The absorption spectrum of the trinuclear complex has been fit to a model, which includes a solvent broadening parameter. Based on this fit, the total reorganization energy of the photoinduced intervalent electron transfer has been calculated to be approximately 75% outer sphere.

Original languageEnglish (US)
Pages (from-to)177-194
Number of pages18
JournalCoordination Chemistry Reviews
Volume211
Issue number1
DOIs
StatePublished - Jan 1 2001

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Keywords

  • Electronic coupling
  • Mixed-valence complex
  • Resonance Raman
  • Solvent broadening

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