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Title: Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy

Abstract

The ultraviolet-induced photochemistry of five-membered heterocyclic rings often involves ring opening as a prominent excited-state relaxation pathway. The identification of this particular photoinduced mechanism, however, presents a challenge for many experimental methods. We show that femtosecond X-ray transient absorption spectroscopy at the carbon K-edge (~284 eV) provides core-to-valence spectral fingerprints that enable the unambiguous identification of ring-opened isomers of organic heterocycles. The unique differences in the electronic structure between a carbon atom bonded to the oxygen in the ring versus a carbon atom set free of the oxygen in the ring-opened product are readily apparent in the X-ray spectra. Ultrafast ring opening via C-O bond fission occurs within ~350 fs in 266-nm photoexcited furfural, as evidenced by fingerprint core (carbon 1s) electronic transitions into a nonbonding orbital of the open-chain carbene intermediate at 283.3 eV. The lack of recovery of the 1sπ* ground-state depletion in furfural at 286.4 eV indicates that internal conversion to the ground state is a minor channel. These experimental results, augmented by recent advances in the generation of isolated attosecond pulses at the carbon K-edge, will pave the way for probing ring-opened conical intersection dynamics in the future.

Authors:
 [1];  [1];  [2]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Ludwig Maximilian Univ., Munich (Germany)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1580334
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 39; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bhattacherjee, Aditi, Schnorr, Kirsten, Oesterling, Sven, Yang, Zheyue, Xue, Tian, de Vivie-Riedle, Regina, and Leone, Stephen R. Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy. United States: N. p., 2018. Web. doi:10.1021/jacs.8b07155.
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Bhattacherjee, Aditi, Schnorr, Kirsten, Oesterling, Sven, Yang, Zheyue, Xue, Tian, de Vivie-Riedle, Regina, & Leone, Stephen R. Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy. United States. https://doi.org/10.1021/jacs.8b07155
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Bhattacherjee, Aditi, Schnorr, Kirsten, Oesterling, Sven, Yang, Zheyue, Xue, Tian, de Vivie-Riedle, Regina, and Leone, Stephen R. Tue . "Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy". United States. https://doi.org/10.1021/jacs.8b07155. https://www.osti.gov/servlets/purl/1580334.
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@article{osti_1580334,
title = {Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy},
author = {Bhattacherjee, Aditi and Schnorr, Kirsten and Oesterling, Sven and Yang, Zheyue and Xue, Tian and de Vivie-Riedle, Regina and Leone, Stephen R.},
abstractNote = {The ultraviolet-induced photochemistry of five-membered heterocyclic rings often involves ring opening as a prominent excited-state relaxation pathway. The identification of this particular photoinduced mechanism, however, presents a challenge for many experimental methods. We show that femtosecond X-ray transient absorption spectroscopy at the carbon K-edge (~284 eV) provides core-to-valence spectral fingerprints that enable the unambiguous identification of ring-opened isomers of organic heterocycles. The unique differences in the electronic structure between a carbon atom bonded to the oxygen in the ring versus a carbon atom set free of the oxygen in the ring-opened product are readily apparent in the X-ray spectra. Ultrafast ring opening via C-O bond fission occurs within ~350 fs in 266-nm photoexcited furfural, as evidenced by fingerprint core (carbon 1s) electronic transitions into a nonbonding orbital of the open-chain carbene intermediate at 283.3 eV. The lack of recovery of the 1sπ* ground-state depletion in furfural at 286.4 eV indicates that internal conversion to the ground state is a minor channel. These experimental results, augmented by recent advances in the generation of isolated attosecond pulses at the carbon K-edge, will pave the way for probing ring-opened conical intersection dynamics in the future.},
doi = {10.1021/jacs.8b07155},
journal = {Journal of the American Chemical Society},
number = 39,
volume = 140,
place = {United States},
year = {Tue Sep 11 00:00:00 EDT 2018},
month = {Tue Sep 11 00:00:00 EDT 2018}
}
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https://doi.org/10.1021/jacs.8b07155
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