Photochemical image generation in a cyanogel system synthesized from tetrachloropalladate(II) and the trimetallic mixed-valence complex [(NC)5FeII-CN-PtIV (NH3)4-NC-FeII (CN)5]4-: Consideration of photochemical and dark mechanistic pathways of Prussian blue formation

David F. Watson, Jennifer L. Willson, Andrew Bruce Bocarsly

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Abstract

The cyanogel system involving PdCl42- and the mixed-valence complex [(NC)5FeII-CN-PtIV (NH3)4-NC-FeII (CN)5]4-is reported. The system has been characterized by UV-vis absorption, diffuse reflectance infrared, and resonance Raman spectroscopies. Gelation occurs through coordination of Pd(II) to the nitrogen atom of terminal cyanide ligands in the mixed-valence complex. Irradiation into the Fe(II) → Pt(IV) intervalent electron transfer (IT) band of [(NC)5FeII-CN-PtIV (NH3)4-NC-FeII (CN)5]4-results in the formation of a variety of Prussian-blue-like species within the rigid cyanogel matrix. Photochemical and dark mechanisms involving coupled cyanide loss and Fe(II) oxidation are proposed for the formation of Prussian-blue-like species. The optical contrast between irradiated and nonirradiated regions of the gel enables photochemical image generation with at least 12 μm resolution. This capability is demonstrated through the production of a series of diffraction gratings in cyanogel samples.

Original languageEnglish (US)
Pages (from-to)2408-2416
Number of pages9
JournalInorganic Chemistry
Volume41
Issue number9
DOIs
StatePublished - May 6 2002

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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