Photoelectron Spectroscopy Study of Quinonimides

Ekram Hossain, Shihu M. Deng, Samer Gozem, Anna I. Krylov, Xue Bin Wang, Paul G. Wenthold

Research output: Contribution to journalArticle

6 Scopus citations

Abstract

Structures and energetics of o-, m-, and p-quinonimide anions (OC6H4N-) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, and it is shown that accurate predictions for the electronic structure of the para-quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.

Original languageEnglish (US)
Pages (from-to)11138-11148
Number of pages11
JournalJournal of the American Chemical Society
Volume139
Issue number32
DOIs
StatePublished - Aug 16 2017
Externally publishedYes

ASJC Scopus subject areas

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

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  • Cite this

    Hossain, E., Deng, S. M., Gozem, S., Krylov, A. I., Wang, X. B., & Wenthold, P. G. (2017). Photoelectron Spectroscopy Study of Quinonimides. Journal of the American Chemical Society, 139(32), 11138-11148. https://doi.org/10.1021/jacs.7b05197