TY - JOUR
T1 - Correlation between bowl-inversion energy and bowl depth in substituted sumanenes
AU - Shrestha, Binod Babu
AU - Karanjit, Sangita
AU - Higashibayashi, Shuhei
AU - Sakurai, Hidehiro
N1 - Funding Information:
Acknowledgments: We acknowledge financial support from JST(ACT-C) and MEXT. The computational study was supported by the Research Center for Computational Science, Okazaki, Japan.
PY - 2014/5
Y1 - 2014/5
N2 - The correlation between the bowl-inversion energy and the bowl depth for sumanenes monosubstituted with an iodo, formyl, or nitro group was investigated experimentally and by theoretical calculations. The bowl-inversion energies of the substituted sumanenes were determined experimentally by two-dimensional NMR exchange spectroscopy measurements. Various density functional theory methods were examined for the calculation of the structure and the bowl-inversion energy of sumanene, and it was found that PBE0, wB97XD, and M06-2X gave better fits of the experimental value than did B3LYP. The experimental value was well reproduced at these levels of theory. The bowl structures and bowl-inversion energies of monosubstituted sumanenes were therefore calculated at the wB97XD/6-311+G(d,p) level of theory. In both the experiments and the calculations, the correlation followed the equation E = acos4θ , where a is a coefficient, E is the bowl-inversion energy, and cos θ is the normalized bowl depth, indicating that the bowl inversion follows a double-well potential energy diagram.
AB - The correlation between the bowl-inversion energy and the bowl depth for sumanenes monosubstituted with an iodo, formyl, or nitro group was investigated experimentally and by theoretical calculations. The bowl-inversion energies of the substituted sumanenes were determined experimentally by two-dimensional NMR exchange spectroscopy measurements. Various density functional theory methods were examined for the calculation of the structure and the bowl-inversion energy of sumanene, and it was found that PBE0, wB97XD, and M06-2X gave better fits of the experimental value than did B3LYP. The experimental value was well reproduced at these levels of theory. The bowl structures and bowl-inversion energies of monosubstituted sumanenes were therefore calculated at the wB97XD/6-311+G(d,p) level of theory. In both the experiments and the calculations, the correlation followed the equation E = acos4θ , where a is a coefficient, E is the bowl-inversion energy, and cos θ is the normalized bowl depth, indicating that the bowl inversion follows a double-well potential energy diagram.
KW - Aromatic compounds
KW - Bowl inversion
KW - Buckybowls
KW - NMS-IX
KW - Organic chemistry
KW - Polycyclic aromatics
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U2 - 10.1515/pac-2013-1212
DO - 10.1515/pac-2013-1212
M3 - Article
AN - SCOPUS:84900840088
SN - 0033-4545
VL - 86
SP - 747
EP - 753
JO - Pure and Applied Chemistry
JF - Pure and Applied Chemistry
IS - 5
ER -