Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X-ray Absorption Spectroscopy at the Sulfur K-Edge

Miguel Ochmann, Inga Von Ahnen, Amy A. Cordones, Abid Hussain, Jae Hyuk Lee, Kiryong Hong, Katrin Adamczyk, Oriol Vendrell, Tae Kyu Kim, Robert W. Schoenlein, Nils Huse

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

We applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ∼70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemical reaction pathways and transient products of sulfur-containing molecules in solution.

Original languageEnglish
Pages (from-to)4797-4804
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number13
DOIs
Publication statusPublished - 2017 Apr 5

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X-Ray Absorption Spectroscopy
X ray absorption spectroscopy
Isomerization
Sulfur
Sulfhydryl Compounds
Light
Absorption spectroscopy
Thiones
Spectrum Analysis
Chemical reactions
Radiation
Regioselectivity
Synchrotrons
Synchrotron radiation
Lighting
Isomers
Electronic structure
Molecules

All Science Journal Classification (ASJC) codes

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

Cite this

Ochmann, Miguel ; Von Ahnen, Inga ; Cordones, Amy A. ; Hussain, Abid ; Lee, Jae Hyuk ; Hong, Kiryong ; Adamczyk, Katrin ; Vendrell, Oriol ; Kim, Tae Kyu ; Schoenlein, Robert W. ; Huse, Nils. / Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X-ray Absorption Spectroscopy at the Sulfur K-Edge. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 13. pp. 4797-4804.
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abstract = "We applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ∼70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemical reaction pathways and transient products of sulfur-containing molecules in solution.",
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Ochmann, M, Von Ahnen, I, Cordones, AA, Hussain, A, Lee, JH, Hong, K, Adamczyk, K, Vendrell, O, Kim, TK, Schoenlein, RW & Huse, N 2017, 'Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X-ray Absorption Spectroscopy at the Sulfur K-Edge', Journal of the American Chemical Society, vol. 139, no. 13, pp. 4797-4804. https://doi.org/10.1021/jacs.6b12992

Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X-ray Absorption Spectroscopy at the Sulfur K-Edge. / Ochmann, Miguel; Von Ahnen, Inga; Cordones, Amy A.; Hussain, Abid; Lee, Jae Hyuk; Hong, Kiryong; Adamczyk, Katrin; Vendrell, Oriol; Kim, Tae Kyu; Schoenlein, Robert W.; Huse, Nils.

In: Journal of the American Chemical Society, Vol. 139, No. 13, 05.04.2017, p. 4797-4804.

Research output: Contribution to journalArticle

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AU - Cordones, Amy A.

AU - Hussain, Abid

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AU - Huse, Nils

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