Сибирский федеральный университет

Тип публикации: статья из журнала

Год издания: 2022

Идентификатор DOI: 10.1021/acs.jpclett.2c02659

Аннотация: Although cyclo[18]carbon has been isolated experimentally from two precursors, C18Br6and 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 C18Br6compared to C18(CO)6, confirming a considerably higher yield of cylco[18]carbon when the C18Br6precursor 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. © 2022 American Chemical Society. All rights reserved.

Журнал: Journal of Physical Chemistry Letters

Выпуск журнала: Vol. 13, Is. 44

Номера страниц: 10318-10325

ISSN журнала: 19487185

Издатель: American Chemical Society

• Suresh R. (International Research Center of Spectroscopy and Quantum Chemistry - IRC SQC, Siberian Federal University, 79 Svobodny pr., Krasnoyarsk, 660041, Russian Federation)
• Baryshnikov G.V. (Laboratory of Organic Electronics, Department of Science and Technology, Linköping University, Norrköping, 60174, Sweden)
• Kuklin A.V. (Division of X-ray Photon Science, Department of Physics and Astronomy, Uppsala University, Box 516, Uppsala, SE-751 20, Sweden)
• Nemkova D.I. (International Research Center of Spectroscopy and Quantum Chemistry - IRC SQC, Siberian Federal University, 79 Svobodny pr., Krasnoyarsk, 660041, Russian Federation, Division of Physical and Inorganic Chemistry, Institute of Non-ferrous Metals, Siberian Federal University, 79 Svobodny pr., Krasnoyarsk, 660041, Russian Federation)
• Saikova S.V. (Division of Physical and Inorganic Chemistry, Institute of Non-ferrous Metals, Siberian Federal University, 79 Svobodny pr., Krasnoyarsk, 660041, Russian Federation)
• Ågren H. (Division of X-ray Photon Science, Department of Physics and Astronomy, Uppsala University, Box 516, Uppsala, SE-751 20, Sweden)

• Scopus