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Title: The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction

Abstract

The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. With this work, we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subångström length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon–carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We discovered a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [2];  [3];  [4];  [1];  [1];  [5]; ORCiD logo [2]; ORCiD logo [6];  [7];  [8]; ORCiD logo [7];  [7];  [7]; ORCiD logo [8];  [4]; ORCiD logo [8];  [7] more »; ORCiD logo [7]; ORCiD logo [7]; ORCiD logo [9] « less
+ Show Author Affiliations
  1. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
  2. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Stanford Univ., CA (United States)
  3. Univ. of York (United Kingdom); Univ. of Nebraska, Lincoln, NE (United States)
  4. Univ. of Nebraska, Lincoln, NE (United States)
  5. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Universität Potsdam, Potsdam (Germany)
  6. Univ. of Edinburgh, Scotland (United Kingdom)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  8. Brown Univ., Providence, RI (United States)
  9. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1513333
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 11; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wolf, Thomas J. A., Sanchez, D. M., Yang, J., Parrish, R. M., Nunes, J. P. F., Centurion, M., Coffee, R., Cryan, J. P., Gühr, M., Hegazy, K., Kirrander, A., Li, R. K., Ruddock, J., Shen, X., Vecchione, T., Weathersby, S. P., Weber, P. M., Wilkin, K., Yong, H., Zheng, Q., Wang, X. J., Minitti, M. P., and Martínez, Todd J. The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction. United States: N. p., 2019. Web. doi:10.1038/s41557-019-0252-7.
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Wolf, Thomas J. A., Sanchez, D. M., Yang, J., Parrish, R. M., Nunes, J. P. F., Centurion, M., Coffee, R., Cryan, J. P., Gühr, M., Hegazy, K., Kirrander, A., Li, R. K., Ruddock, J., Shen, X., Vecchione, T., Weathersby, S. P., Weber, P. M., Wilkin, K., Yong, H., Zheng, Q., Wang, X. J., Minitti, M. P., & Martínez, Todd J. The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction. United States. https://doi.org/10.1038/s41557-019-0252-7
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Wolf, Thomas J. A., Sanchez, D. M., Yang, J., Parrish, R. M., Nunes, J. P. F., Centurion, M., Coffee, R., Cryan, J. P., Gühr, M., Hegazy, K., Kirrander, A., Li, R. K., Ruddock, J., Shen, X., Vecchione, T., Weathersby, S. P., Weber, P. M., Wilkin, K., Yong, H., Zheng, Q., Wang, X. J., Minitti, M. P., and Martínez, Todd J. Mon . "The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction". United States. https://doi.org/10.1038/s41557-019-0252-7. https://www.osti.gov/servlets/purl/1513333.
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@article{osti_1513333,
title = {The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction},
author = {Wolf, Thomas J. A. and Sanchez, D. M. and Yang, J. and Parrish, R. M. and Nunes, J. P. F. and Centurion, M. and Coffee, R. and Cryan, J. P. and Gühr, M. and Hegazy, K. and Kirrander, A. and Li, R. K. and Ruddock, J. and Shen, X. and Vecchione, T. and Weathersby, S. P. and Weber, P. M. and Wilkin, K. and Yong, H. and Zheng, Q. and Wang, X. J. and Minitti, M. P. and Martínez, Todd J.},
abstractNote = {The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. With this work, we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subångström length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon–carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We discovered a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.},
doi = {10.1038/s41557-019-0252-7},
journal = {Nature Chemistry},
number = ,
volume = 11,
place = {United States},
year = {Mon Apr 15 00:00:00 EDT 2019},
month = {Mon Apr 15 00:00:00 EDT 2019}
}
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https://doi.org/10.1038/s41557-019-0252-7
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