ORCID
- Rahul Suresh: 0000-0002-6354-0886
Abstract
Although cyclo[18]carbon has been isolated experimentally from two precursors, C18Br6 and C18(CO)6, no reaction mechanisms have yet been explored. Herein, we provide insight into the mechanism behind debromination and decarbonylation. Both neutral precursors demonstrate high activation barriers of ∼2.3 eV, while the application of an electric field can lower the barriers by 0.1–0.2 eV. The barrier energy of the anion-radicals is found to be significantly lower for C18Br6 compared to C18(CO)6, confirming a considerably higher yield of cylco[18]carbon when the C18Br6 precursor is used. Elongation of the C–Br bond in the anion-radical confirms its predissociation condition. Natural bonding orbital analysis shows that the stability of C–Br and C–CO bonds in the anion-radicals is lower compared to their neutral species, indicating a possible higher yield. The applied analysis provides crucial details regarding the reaction yield of cyclo[18]carbon and can serve as a general scheme for tuning reaction conditions for other organic precursors.
DOI Link
Publication Date
2022-11-10
Publication Title
Journal of Physical Chemistry Letters
Volume
13
Issue
44
First Page
10318
Last Page
10325
Deposit Date
2026-07-29
Funding
We thank Prof. Y. Yamada at the University of Tsukuba for discussion of the STM technique. R.S. and D.I.N. acknowledge support from the Ministry of Science and Higher Education of the Russian Federation (FSRZ-2020-0008). G.V.B. acknowledges support from the Swedish Research Council (Starting Grant No. 2020-04600). G.V.B., A.V.K., and H.Å. thank the Swedish National Infrastructure for Computing (SNIC 2021-3-22 and SNIC 2022-5-103) at the National Supercomputer Centre of Linköping University and High-Performance Computing Center North (Sweden) partially funded by the Swedish Research Council through Grant Agreement No. 2018-05973.
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.
Additional Links
Recommended Citation
Suresh, Rahul; Baryshnikov, Glib; Kuklin, Artem V.; Nemkova, Diana I.; Saikova, Svetlana V.; and Ågren, Hans, "Cyclo[18]carbon Formation from C18Br6 and C18(CO)6 Precursors" (2022). Research Outputs: 2025-Present. 24.
https://arrow.tudublin.ie/scschphyro/24