Interfacial photoannealing: The light driven alteration of the surface-binding geometry of a mixed-valence complex capable of multielectron charge transfer on colloidal TiO2

David F. Watson, Andrew Bruce Bocarsly

Research output: Contribution to journalArticle

1 Scopus citations

Abstract

The trimetallic, mixed-valence complex [(NC)5FeII-CN-PtIV(NH3) 4-NC-FeII(CN)5]4- was surface-attached to colloidal TiC. The system was characterized by UV/vis absorption, diffuse reflectance IR, and resonance Raman spectroscopies. The surface-bound complex absorbed at 400 nm, corresponding to Fe(II) → Pt(IV) intervalent electron transfer. Exhaustive irradiation into this band resulted in a broadening of the visible absorption band and a change in the bridging cyanide stretching bands of the resonance Raman spectrum. The distribution of bridging cyanide Raman intensities in the exhaustively irradiated sample was found to vary with incident wavelength. The UV/vis absorption and resonance Raman spectral changes are explained in terms of a rearrangement of the surface-binding geometry of the complex, resulting in the selectivity of electron-transfer direction within the complex. Irradiation of Fe(CN)o3~ in the presence of TiU2 with visible light resulted in the photoreduction of Fe(CN)63- to Fe(CN)64-. This photoreduction is believed to occur by direct TiO2(VB) → Fe(t2g) photoinduced electron transfer, rather than electron transfer from photoexcited TiO2 to Fe(CN)63-.

Original languageEnglish (US)
Pages (from-to)10940-10948
Number of pages9
JournalJournal of Physical Chemistry B
Volume104
Issue number46
DOIs
StatePublished - Nov 23 2000

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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