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

Research output: Contribution to journalArticle

19 Citations (Scopus)

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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Ruthenium
Charge transfer
Metals
Ligands
Stark effect
Electrons
Cations
Crystal structure
X rays
Glass
bis(bipyridyl)ruthenium(II)

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

The effective electron-transfer distance in dinuclear ruthenium complexes containing the unsymmetrical bridging ligand 3,5-bis(2-pyridyl)-1,2,4-triazolate. / D'Alessandro, Deanna M.; Dinolfo, Peter H.; Hupp, Joseph T; Junk, Peter C.; Keene, F. Richard.

In: European Journal of Inorganic Chemistry, No. 4, 20.02.2006, p. 772-783.

Research output: Contribution to journalArticle

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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 {\AA} for the ΔΛ/ΛΔ form and 5.44 ± 0.04 {\AA} for the ΔΔ/ ΛΛ form. These values correspond to approximately 95 and 88{\%}, respectively, of the geometrical metal-metal distance of 6.185(10) {\AA}, 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.",
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T1 - The effective electron-transfer distance in dinuclear ruthenium complexes containing the unsymmetrical bridging ligand 3,5-bis(2-pyridyl)-1,2,4-triazolate

AU - D'Alessandro, Deanna M.

AU - Dinolfo, Peter H.

AU - Hupp, Joseph T

AU - Junk, Peter C.

AU - Keene, F. Richard

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AB - 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.

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