Photochemical charge separation within aromatic hydrazines and the effect of excited-state intervalence in dihydrazines

Stephen F. Nelsen, Asgeir E. Konradsson, Michael N. Weaver, Ilia A. Guzei, Mark Goebel, Rüdiger Wortmann, Jenny V. Lockard, Jeffrey I. Zink

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Abstract

Photolysis into the longest wavelength absorption band of 2-tert-butyl-2,3-diazabicyclo[2.2.2]oct-3-yl hydrazine (Hy) substituted naphthalenes causes aryl group reduction electron transfer to give +Hy-Ar -. Electrooptical absorption measurements characterize the charge separation properties from these bands. Emission studies demonstrate that the separation between absorption and emission maxima for symmetrically disubstituted compounds is smaller than that for monosubstituted compounds, which is attributed to excited-state intervalence. The excited-state diabatic surfaces may be described as a Hy +-NA - -Hy 0, Hy 0-NA --Hy + pair, for which electronic interaction produces a double minimum that qualitatively resembles that in the ground state of the disubstituted intervalence radical cations.

Original languageEnglish (US)
Pages (from-to)10854-10861
Number of pages8
JournalJournal of Physical Chemistry A
Volume109
Issue number48
DOIs
StatePublished - Dec 8 2005
Externally publishedYes

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Nelsen, S. F., Konradsson, A. E., Weaver, M. N., Guzei, I. A., Goebel, M., Wortmann, R., Lockard, J. V., & Zink, J. I. (2005). Photochemical charge separation within aromatic hydrazines and the effect of excited-state intervalence in dihydrazines. Journal of Physical Chemistry A, 109(48), 10854-10861. https://doi.org/10.1021/jp052702m