Optical electron transfer in mixed solvents. Major energetic effects from unsymmetrical secondary coordination

Joseph T Hupp, Jane Weydert

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Abstract

Optical electron transfer in the symmetrical, mixed-valence dimer [(NH3)5RuII(4,4′-bpy)Ru III(NH3)5]5+ (4,4′-bpy is 4,4′-bipyridine) has been examined in mixtures of acetonitrile and dimethyl sulfoxide (Me2SO) as solvent. From spectral and electrochemical measurements evidence was found for strong selective solvation by Me2SO. For the metal-to-metal charge-transfer transition, unexpectedly large energetic effects were observed for the Me2SO mole fraction range between 0 and ∼0.1. The energetic effects were found to result from unsymmetrical secondary coordination for (NH3)5RuIII vs. (NH3)5RuII. The appearance of such effects suggests the existence of parallel rate effects for related thermal self-exchanges.

Original languageEnglish
Pages (from-to)2657-2660
Number of pages4
JournalInorganic Chemistry
Volume26
Issue number16
Publication statusPublished - 1987

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ASJC Scopus subject areas

  • Inorganic Chemistry

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