Resonance Raman and semiempirical electronic structure studies of an odd-electron dinickel tetraiminoethylenedimacrocycle complex

Gerald M. Sando, Anandhi Ray, Larry O. Spreer, Kenneth G. Spears, Joseph T Hupp

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Resonance Raman studies of Ni2TIED3+ (TIED = tetraiminoethylenedimacrocycle) reveal that many modes couple to the intense electronic transition centered at 725 nm, a feature that is nominally similar to the intense delocalized intervalence absorption bands observed in the same region for Fe2(TIED)L45+ and Ru2(TIED)L45+ (L is any of several axial ligands). Time-dependent spectral modeling of the Raman and absorption spectra for the nickel compound was undertaken to understand the electronic transition. We were unable to model the Raman and absorption spectra successfully with a single electronic transition, suggesting that the absorption band is made up of two overlapping transitions. Semiempirical electronic structure calculations corroborate the suggestion. Additionally, these calculations indicate that the transitions are in fact ligand-localized transitions, with little metal involvement and no charge-transfer character. Furthermore, the ground-state electronic structure is best described as an identical pair of Ni(II) centers bridged by a radical anion rather than a three-site mixed-valence assembly. Previous EPR studies (McAuley and Xu, Inorg. Chem. 1992, 31, 5549) had indicated primarily ligand character for the radical. The assignments are consistent with the resonance Raman results where the dominant modes coupled to the transitions are assigned as totally symmetric bridge vibrations.

Original languageEnglish
Pages (from-to)3911-3914
Number of pages4
JournalInorganic Chemistry
Volume39
Issue number17
DOIs
Publication statusPublished - Aug 21 2000

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Electronic structure
Absorption spectra
electronic structure
Electrons
Electron transitions
Ligands
Raman scattering
electrons
absorption spectra
Nickel compounds
ligands
Ground state
Anions
Paramagnetic resonance
Charge transfer
electronics
nickel compounds
Raman spectra
Metals
coupled modes

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Resonance Raman and semiempirical electronic structure studies of an odd-electron dinickel tetraiminoethylenedimacrocycle complex. / Sando, Gerald M.; Ray, Anandhi; Spreer, Larry O.; Spears, Kenneth G.; Hupp, Joseph T.

In: Inorganic Chemistry, Vol. 39, No. 17, 21.08.2000, p. 3911-3914.

Research output: Contribution to journalArticle

Sando, Gerald M. ; Ray, Anandhi ; Spreer, Larry O. ; Spears, Kenneth G. ; Hupp, Joseph T. / Resonance Raman and semiempirical electronic structure studies of an odd-electron dinickel tetraiminoethylenedimacrocycle complex. In: Inorganic Chemistry. 2000 ; Vol. 39, No. 17. pp. 3911-3914.
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