The effective electron-transfer distance in dinuclear ruthenium complexes containing the unsymmetrical bridging ligand 3,5-bis(2-pyridyl)-1,2,4-triazolate

Deanna M. D'Alessandro, Peter H. Dinolfo, Joseph T. Hupp, Peter C. Junk, F. Richard Keene

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Abstract

Electroabsorption (Stark effect) measurements on the intervalence charge-transfer (IVCT) transitions in the diastereoisomers of [{Ru(bpy) 2}2(μ-bpt-)]4+ [bpy = 2,2′-bipyridine, bpt- = 3,5-bis(2-pyridyl)-1,2,4-triazolate] in n-butyronitrile glass at 77 K reveal effective charge-transfer distances of 5.92 ± 0.03 Å for the ΔΛ/ΛΔ form and 5.44 ± 0.04 Å for the ΔΔ/ ΛΛ form. These values correspond to approximately 95 and 88%, respectively, of the geometrical metal-metal distance of 6.185(10) Å, obtained from the X-ray crystal structure of the cation in the related complex (ΔΛ)-[{Ru(Me 2bpy)2}2(μ-bpt-)](PF 6)3. The results are consistent with a localized Class II classification for the mixed-valence systems [{Ru(pp)2} 2(μ-bpt-)]4+, where pp = bpy, Me 2bpy = 4,4′-dimethyl-2,2′-bipyridine.

Original languageEnglish
Pages (from-to)772-783
Number of pages12
JournalEuropean Journal of Inorganic Chemistry
Issue number4
DOIs
Publication statusPublished - Feb 20 2006

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Keywords

  • Dinuclear
  • Electron transfer
  • Mixed-valent compounds
  • Ruthenium
  • Stark spectroscopy
  • Stereochemistry
  • Through-bond interactions

ASJC Scopus subject areas

  • Inorganic Chemistry

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