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

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 illustrated. 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. Thus, 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. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Samara National Research Univ. (Russia)
  4. Samara National Research Univ. (Russia); Florida International Univ., Miami, FL (United States)
Publication Date:
Research Org.:
Univ. of Hawaii, Honolulu, HI (United States); Florida International Univ., Miami, FL (United States); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Ministry of Science and Higher Education of the Russian Federation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1603233
Alternate Identifier(s):
OSTI ID: 1593495; OSTI ID: 1608276
Grant/Contract Number:  
FG02-03ER15411; FG02-04ER15570; AC02-05CH11231; 14.Y26.31.0020
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 10; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; gas-phase chemistry; hydrogen abstraction/vinylacetylene addition (HAVA); interstellar medium; mass spectrometry; polycyclic aromatic hydrocarbons (PAHs)

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. United States: N. p., 2019. Web. https://doi.org/10.1002/anie.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. United States. https://doi.org/10.1002/anie.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. Mon . "A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase". United States. https://doi.org/10.1002/anie.201913037. https://www.osti.gov/servlets/purl/1603233.
@article{osti_1603233,
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 = {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 illustrated. 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. Thus, connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry.},
doi = {10.1002/anie.201913037},
journal = {Angewandte Chemie (International Edition)},
number = 10,
volume = 59,
place = {United States},
year = {2019},
month = {12}
}

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