A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase
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- Department of Chemistry University of Hawaii at Manoa Honolulu HI 96822 USA
- Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
- Samara National Research University Samara 443086 Russia
- Samara National Research University Samara 443086 Russia, Department of Chemistry and Biochemistry Florida International University Miami FL 33199 USA
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.
- Sponsoring Organization:
- USDOE
- Grant/Contract Number:
- AC02-05CH11231; FG02-03ER15411; FG02-04ER15570
- OSTI ID:
- 1593502
- Journal Information:
- Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 10 Vol. 132; ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
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