Structural, Aromatic, Optical and Reactive Features of C12-(CO)n (n = 2, 4, 6): A DFT Study
- 1School of Materials and Chemical Engineering, West Anhui University, Lu’an 237012, China
Abstract
The geometric, electronic, spectroscopic, adsorption, and reactive properties of C12-(CO)n (n = 2, 4, 6) were systematically investigated using density functional theory at the ωB97XD/def2-TZVP level. All three molecules adopt planar structures with pronounced bond length alternation along the C12 skeleton. Multi-index bonding analyses reveal significant π-electron localization at short C–C bonds rather than full-ring delocalization. As the number of OCCO fusion units increases, molecular symmetry evolves from C2v to D2h and further to D3h. Aromaticity assessments using AV1245, HOMA, FLU-π, and ELF-π consistently indicate the absence of global aromaticity; OCCO fusion primarily disrupts πin delocalization while leaving πout conjugation comparatively less affected. Simulated UV-Vis spectra show that increasing OCCO units shifts the dominant absorption band toward the ultraviolet region, with low-energy excitations confirmed as locally excited states dominated by charge redistribution within the C12 ring. vdW potential calculations disclose an anomalous adsorption strength sequence for light noble gases (He > Ne), and it is contrary to the counterpoise-corrected interaction energy results. Local electron attachment energy (LEAE) and orbital-weighted dual descriptor (OWDD) jointly demonstrate that the intrinsic electron-accepting reactivity follows C12-(CO)6 > C12-(CO)4 > C12-(CO)2, qualitatively consistent with LUMO energy lowering yet modulated by electron-attachment relaxation effects. This work provides theoretical insights into the structure–bonding–reactivity relationships of OCCO-fused carbon macrocyclic systems.
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BibTeX
@article{chen2026structural,
title = {{Structural, Aromatic, Optical and Reactive Features of C12-(CO)n (n = 2, 4, 6): A DFT Study}},
author = {Xin Chen and Pei-Pei Li and Guang-Nian Xu},
journal = {Nanomaterials},
year = {2026},
month = oct,
doi = {10.3390/nano16191254},
url = {https://www.mdpi.com/2079-4991/16/19/1254},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Structural, Aromatic, Optical and Reactive Features of C12-(CO)n (n = 2, 4, 6): A DFT Study
AU - Xin Chen
AU - Pei-Pei Li
AU - Guang-Nian Xu
PY - 2026
DA - 2026/10/03
JO - Nanomaterials
DO - 10.3390/nano16191254
UR - https://www.mdpi.com/2079-4991/16/19/1254
AB - The geometric, electronic, spectroscopic, adsorption, and reactive properties of C12-(CO)n (n = 2, 4, 6) were systematically investigated using density functional theory at the ωB97XD/def2-TZVP level. All three molecules adopt planar structures with pronounced bond length alternation along the C12 skeleton. Multi-index bonding analyses reveal significant π-electron localization at short C–C bonds rather than full-ring delocalization. As the number of OCCO fusion units increases, molecular symmetry evolves from C2v to D2h and further to D3h. Aromaticity assessments using AV1245, HOMA, FLU-π, and ELF-π consistently indicate the absence of global aromaticity; OCCO fusion primarily disrupts πin delocalization while leaving πout conjugation comparatively less affected. Simulated UV-Vis spectra show that increasing OCCO units shifts the dominant absorption band toward the ultraviolet region, with low-energy excitations confirmed as locally excited states dominated by charge redistribution within the C12 ring. vdW potential calculations disclose an anomalous adsorption strength sequence for light noble gases (He > Ne), and it is contrary to the counterpoise-corrected interaction energy results. Local electron attachment energy (LEAE) and orbital-weighted dual descriptor (OWDD) jointly demonstrate that the intrinsic electron-accepting reactivity follows C12-(CO)6 > C12-(CO)4 > C12-(CO)2, qualitatively consistent with LUMO energy lowering yet modulated by electron-attachment relaxation effects. This work provides theoretical insights into the structure–bonding–reactivity relationships of OCCO-fused carbon macrocyclic systems.
SN - 2079-4991
ER -