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Title: A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase

Abstract

Abstract A unified low‐temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes—polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho ‐condensed arrangements of fused benzene rings—is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas‐phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer‐selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free‐radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]
  1. Department of Chemistry University of Hawaii at Manoa Honolulu HI 96822 USA
  2. Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
  3. Samara National Research University Samara 443086 Russia
  4. Samara National Research University Samara 443086 Russia, Department of Chemistry and Biochemistry Florida International University Miami FL 33199 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1593502
Grant/Contract Number:  
FG02-03ER15411; FG02-04ER15570; AC02-05CH11231
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Name: Angewandte Chemie Journal Volume: 132 Journal Issue: 10; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Zhao, Long, Kaiser, Ralf I., Xu, Bo, Ablikim, Utuq, Ahmed, Musahid, Evseev, Mikhail M., Bashkirov, Eugene K., Azyazov, Valeriy N., and Mebel, Alexander M. A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase. Germany: N. p., 2020. Web. doi:10.1002/ange.201913037.
Zhao, Long, Kaiser, Ralf I., Xu, Bo, Ablikim, Utuq, Ahmed, Musahid, Evseev, Mikhail M., Bashkirov, Eugene K., Azyazov, Valeriy N., & Mebel, Alexander M. A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase. Germany. https://doi.org/10.1002/ange.201913037
Zhao, Long, Kaiser, Ralf I., Xu, Bo, Ablikim, Utuq, Ahmed, Musahid, Evseev, Mikhail M., Bashkirov, Eugene K., Azyazov, Valeriy N., and Mebel, Alexander M. Thu . "A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase". Germany. https://doi.org/10.1002/ange.201913037.
@article{osti_1593502,
title = {A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase},
author = {Zhao, Long and Kaiser, Ralf I. and Xu, Bo and Ablikim, Utuq and Ahmed, Musahid and Evseev, Mikhail M. and Bashkirov, Eugene K. and Azyazov, Valeriy N. and Mebel, Alexander M.},
abstractNote = {Abstract A unified low‐temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes—polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho ‐condensed arrangements of fused benzene rings—is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas‐phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer‐selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free‐radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry.},
doi = {10.1002/ange.201913037},
journal = {Angewandte Chemie},
number = 10,
volume = 132,
place = {Germany},
year = {Thu Jan 23 00:00:00 EST 2020},
month = {Thu Jan 23 00:00:00 EST 2020}
}

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