Electroabsorption Studies of Metal-to-Ligand Charge Transfer in Ru(phenanthroline)32+

Evidence for Intrinsic Charge Localization in the Initially Formed Excited State

Laba Karki, Joseph T Hupp

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56 Citations (Scopus)

Abstract

Electroabsorption studies of ruthenium(II) tris(phenanthroline) show that a substantial change in dipole moment (|Δμ| = 6.7 ± 1 D) accompanies ground state to "singlet" metal-to-ligand charge transfer (MLCT) excited-state formation. The change is nearly identical to that reported for the 2,2′-bipyridine analogue (Oh; et al. J. Am. Chem. Soc. 1989, 111, 1130). Since both species lack ground-state dipole moments, the finite values for Δμ are diagnostic of intrinsic charge localization in the excited states. The nominally triplet transition for the phenanthroline complex also involves the formation of a charge localized state. The combined results are inconsistent, therefore, with an alternative "delocalized" charge transfer excited-state interpretation suggested by time-resolved resonance Raman studies of the tris(phenanthroline) complex.

Original languageEnglish
Pages (from-to)3318-3321
Number of pages4
JournalInorganic Chemistry
Volume36
Issue number15
Publication statusPublished - 1997

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Phenanthrolines
Excited states
Charge transfer
Metals
charge transfer
Dipole moment
Ligands
Ground state
ligands
dipole moments
metals
excitation
ground state
Ruthenium
Electron transitions
ruthenium
analogs

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Electroabsorption Studies of Metal-to-Ligand Charge Transfer in Ru(phenanthroline)32+: Evidence for Intrinsic Charge Localization in the Initially Formed Excited State",
abstract = "Electroabsorption studies of ruthenium(II) tris(phenanthroline) show that a substantial change in dipole moment (|Δμ| = 6.7 ± 1 D) accompanies ground state to {"}singlet{"} metal-to-ligand charge transfer (MLCT) excited-state formation. The change is nearly identical to that reported for the 2,2′-bipyridine analogue (Oh; et al. J. Am. Chem. Soc. 1989, 111, 1130). Since both species lack ground-state dipole moments, the finite values for Δμ are diagnostic of intrinsic charge localization in the excited states. The nominally triplet transition for the phenanthroline complex also involves the formation of a charge localized state. The combined results are inconsistent, therefore, with an alternative {"}delocalized{"} charge transfer excited-state interpretation suggested by time-resolved resonance Raman studies of the tris(phenanthroline) complex.",
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T1 - Electroabsorption Studies of Metal-to-Ligand Charge Transfer in Ru(phenanthroline)32+

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AU - Hupp, Joseph T

PY - 1997

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N2 - Electroabsorption studies of ruthenium(II) tris(phenanthroline) show that a substantial change in dipole moment (|Δμ| = 6.7 ± 1 D) accompanies ground state to "singlet" metal-to-ligand charge transfer (MLCT) excited-state formation. The change is nearly identical to that reported for the 2,2′-bipyridine analogue (Oh; et al. J. Am. Chem. Soc. 1989, 111, 1130). Since both species lack ground-state dipole moments, the finite values for Δμ are diagnostic of intrinsic charge localization in the excited states. The nominally triplet transition for the phenanthroline complex also involves the formation of a charge localized state. The combined results are inconsistent, therefore, with an alternative "delocalized" charge transfer excited-state interpretation suggested by time-resolved resonance Raman studies of the tris(phenanthroline) complex.

AB - Electroabsorption studies of ruthenium(II) tris(phenanthroline) show that a substantial change in dipole moment (|Δμ| = 6.7 ± 1 D) accompanies ground state to "singlet" metal-to-ligand charge transfer (MLCT) excited-state formation. The change is nearly identical to that reported for the 2,2′-bipyridine analogue (Oh; et al. J. Am. Chem. Soc. 1989, 111, 1130). Since both species lack ground-state dipole moments, the finite values for Δμ are diagnostic of intrinsic charge localization in the excited states. The nominally triplet transition for the phenanthroline complex also involves the formation of a charge localized state. The combined results are inconsistent, therefore, with an alternative "delocalized" charge transfer excited-state interpretation suggested by time-resolved resonance Raman studies of the tris(phenanthroline) complex.

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