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

Zhao, Long; Kaiser, Ralf I.; Xu, Bo; Ablikim, Utuq; Ahmed, Musahid; Evseev, Mikhail M.; Bashkirov, Eugene K.; Azyazov, Valeriy N.; Mebel, Alexander M.

doi:10.1002/anie.201913037

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

Journal Article · 23 December 2019 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201913037 · OSTI ID:1603233

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Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Samara National Research Univ. (Russia)
Samara National Research Univ. (Russia); Florida International Univ., Miami, FL (United States)

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.

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Research Organization:: Univ. of Hawaii, Honolulu, HI (United States); Florida International Univ. (FIU), Miami, FL (United States); University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: 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

Grant/Contract Number:: FG02-03ER15411; FG02-04ER15570; AC02-05CH11231; 14.Y26.31.0020

OSTI ID:: 1603233

Alternate ID(s):: OSTI ID: 1593495; OSTI ID: 1608276

Journal Information:: Angewandte Chemie (International Edition), Vol. 59, Issue 10; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 18 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
gas-phase chemistry
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Title: A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase

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