Underlying spin-orbit coupling structure of intervalence charge transfer bands in dinuclear polypyridyl complexes of ruthenium and osmium

Deanna M. D'Alessandro, Peter H. Dinolfo, Murray S. Davies, Joseph T Hupp, F. Richard Keene

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

The mixed-valence systems meso- and rac-[{M(bpy)2} 2(μ-BL)]5+ {M = Ru, Os; BL = a series of polypyridyl bridging ligands such as 2,3-bis(2-pyridyl)benzoquinoxaline (dpb)} are characterized by multiple intervalence charge transfer (IVCT) and interconfigurational (IC) bands in the mid-infrared and near-infrared (NIR) regions. Differences in the relative energies of the IC transitions for the fully oxidized (+6) states of the osmium systems demonstrate that stereochemical effects lead to fundamental changes in the energy levels of the metal-based dπ orbitals, which are split by spin-orbit coupling and ligand-field asymmetry. An increase in the separation between the IC bands as BL is varied reflects the increase in the degree of electronic coupling through the series of ruthenium and osmium complexes. The increase in the IVCT bandwidths for the former is therefore attributed to the increase in the separation of the three underlying components of the bands. Stark effect measurements reveal small dipole moment changes accompanying IVCT excitation in support of the localized-to-delocalized or delocalized classification for the dinuclear ruthenium and osmium systems.

Original languageEnglish
Pages (from-to)3261-3274
Number of pages14
JournalInorganic Chemistry
Volume45
Issue number8
DOIs
Publication statusPublished - Apr 17 2006

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Osmium
Ruthenium
osmium
ruthenium
Charge transfer
Orbits
charge transfer
orbits
Ligands
Infrared radiation
Stark effect
ligands
Dipole moment
Electron energy levels
dipole moments
energy levels
Metals
asymmetry
bandwidth
valence

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Underlying spin-orbit coupling structure of intervalence charge transfer bands in dinuclear polypyridyl complexes of ruthenium and osmium. / D'Alessandro, Deanna M.; Dinolfo, Peter H.; Davies, Murray S.; Hupp, Joseph T; Keene, F. Richard.

In: Inorganic Chemistry, Vol. 45, No. 8, 17.04.2006, p. 3261-3274.

Research output: Contribution to journalArticle

D'Alessandro, Deanna M. ; Dinolfo, Peter H. ; Davies, Murray S. ; Hupp, Joseph T ; Keene, F. Richard. / Underlying spin-orbit coupling structure of intervalence charge transfer bands in dinuclear polypyridyl complexes of ruthenium and osmium. In: Inorganic Chemistry. 2006 ; Vol. 45, No. 8. pp. 3261-3274.
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