Excited-state mixed-valence distortions in a diisopropyl diphenyl hydrazine cation

Jenny V. Lockard, Jeffrey I. Zink, Yun Luo, Michael N. Weaver, Asgeir E. Konradsson, Joseph W. Fowble, Stephen F. Nelsen

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

Excited-state mixed valence (ESMV) occurs in the 1,2-diphenyl-1,2- diisopropyl hydrazine radical cation, a molecule in which the ground state has a symmetrical charge distribution localized primarily on the hydrazine, but the phenyl to hydrazine charge-transfer excited state has two interchangeably equivalent phenyl groups that have different formal oxidation states. Electronic absorption and resonance Raman spectra are presented. The neighboring orbital model is employed to interpret the absorption spectrum and coupling. Resonance Raman spectroscopy is used to determine the excited-state distortions. The frequencies of the enhanced modes from the resonance Raman spectra are used together with the time-dependent theory of spectroscopy to fit the two observed absorption bands that have resolved vibronic structure. The origins of the vibronic structure and relationships with the neighboring orbital model are discussed.

Original languageEnglish (US)
Pages (from-to)16524-16531
Number of pages8
JournalJournal of the American Chemical Society
Volume128
Issue number51
DOIs
StatePublished - Dec 27 2006
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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