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 journalArticlepeer-review

20 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

Bibliographical note

Funding Information:
This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, the Chemical Sciences, Geosciences, and Biosciences Division under the Department of Energy, Contract No. DE-AC02-05CH11231 (A.A.C., K.H., J.H.L., and R.W.S.). This research was supported by Basic Science Research Program (2013S1A2A2035406, 2014R1A4A1001690 and 2016R1E1A1A01941978) and in part by the Max Planck POSTECH/KOREA Research Initiative Program (2016K1A4A4A01922028) through the National Research Foundation of Korea (NRF) funded by Ministry of Science, ICT and Future Planning (T.K.K. and K.H.). M.O., I.v.A., K.A., and N.H. acknowledge funding from the Max Planck Society and the City of Hamburg. M.O. and N.H. gratefully acknowledge financial support of this work through the Deutsche Forschungsgemeinschaft within the Sonderforschungsbereich 925 ?Light induced dynamics and control of correlated quantum systems?. This research used resources of the Advanced Light Source (LBNL), which is a DOE Office of Science User Facility. The authors would like to thank Bruce Rude for his continuous support of the experimental hardware.

Publisher Copyright:
© 2017 American Chemical Society.

All Science Journal Classification (ASJC) codes

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

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