Optical Electron Transfer in Mixed Solvents. Major Energetic Effects from Unsymmetrical Secondary Coordination

Joseph T. Hupp; Jane Weydert

doi:10.1021/ic00263a021

Optical Electron Transfer in Mixed Solvents. Major Energetic Effects from Unsymmetrical Secondary Coordination

Joseph T. Hupp^*, Jane Weydert

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

Optical electron transfer in the symmetrical, mixed-valence dimer [(NH3)₅Ru^II(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)₅Ru^IIIvs. (NH₃)₅Ru^II. The appearance of such effects suggests the existence of parallel rate effects for related thermal self-exchanges.

Original language	English (US)
Pages (from-to)	2657-2660
Number of pages	4
Journal	Inorganic chemistry
Volume	26
Issue number	16
DOIs	https://doi.org/10.1021/ic00263a021
State	Published - Aug 1 1987

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Optical Electron Transfer in Mixed Solvents. Major Energetic Effects from Unsymmetrical Secondary Coordination",

abstract = "Optical electron transfer in the symmetrical, mixed-valence dimer [(NH3)5RuII(4,4/-bpy)RuIII(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)5RuIIIvs. (NH3)5RuII. The appearance of such effects suggests the existence of parallel rate effects for related thermal self-exchanges.",

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year = "1987",

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T1 - Optical Electron Transfer in Mixed Solvents. Major Energetic Effects from Unsymmetrical Secondary Coordination

AU - Hupp, Joseph T.

AU - Weydert, Jane

PY - 1987/8/1

Y1 - 1987/8/1

N2 - Optical electron transfer in the symmetrical, mixed-valence dimer [(NH3)5RuII(4,4/-bpy)RuIII(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)5RuIIIvs. (NH3)5RuII. The appearance of such effects suggests the existence of parallel rate effects for related thermal self-exchanges.

AB - Optical electron transfer in the symmetrical, mixed-valence dimer [(NH3)5RuII(4,4/-bpy)RuIII(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)5RuIIIvs. (NH3)5RuII. The appearance of such effects suggests the existence of parallel rate effects for related thermal self-exchanges.

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Optical Electron Transfer in Mixed Solvents. Major Energetic Effects from Unsymmetrical Secondary Coordination

Abstract

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