Stability and Reactivity of the Phenalene and Olympicene Isomers

0578700 - ÚOCHB 2024 RIV US eng J - Journal Article
Ferrão, L. F. A. - Pontes, M. A. P. - Fernandes, G. F. S. - Bettanin, F. - Aquino, A. J. A. - Lischka, H. - Nachtigallová, Dana - Machado, F. B. C.
Stability and Reactivity of the Phenalene and Olympicene Isomers.
Journal of Physical Chemistry A. Roč. 127, č. 45 (2023), s. 9430-9441. ISSN 1089-5639. E-ISSN 1520-5215
R&D Projects: GA ČR(CZ) GX19-27454X
Institutional support: RVO:61388963
Keywords : polycyclic aromatic hydrocarbons * perturbation theory * basis sets
OECD category: Inorganic and nuclear chemistry
Impact factor: 2.9, year: 2022
Method of publishing: Limited access
https://doi.org/10.1021/acs.jpca.3c04331

The phenalene (triangulene) and olympicene molecules belong to the polycyclic aromatic hydrocarbon class, which have attracted substantial technological interest due to their unique electronic properties. Electronic structure calculations serve as a valuable tool in investigating the stability and reactivity of these molecular systems. In the present work, the multireference calculations, namely, the complete active space second-order perturbation theory and multireference averaged quadratic coupled cluster (MR-AQCC), were employed to study the reactivity and stability of phenalene and olympicene isomers, as well as their modified structures where the sp3-carbon at the borders were removed. The harmonic oscillator model of aromaticity (HOMA) and the nucleus-independent chemical shift as geometric and magnetic indexes calculated with density functional theory were utilized to assess the aromaticity of the studied molecules. These indexes were compared with properties such as the excitation energy and natural orbitals occupation. The reactivity analyzed using the HOMA index combined with MR-AQCC revealed the radical character of certain structures as well as the weakening of their aromaticity. Moreover, the results suggest that the removal of sp3-carbon atoms and the addition of hydrogen atoms did not alter the π network and the excitation energies of the phenalene molecules.
Permanent Link: https://hdl.handle.net/11104/0347612