Theoretical Investigation into the Structural, Thermochemical, and Electronic Properties of the Decathio[10]circulene

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• 作者：Brian Napolion ; Frank Hagelberg ; Ming-Ju Huang ; John D. Watts ; T. M. Simeon ; Derricka Vereen ; Wilbur L. Walters ; Quinton L. Williams
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：August 11, 2011
• 年：2011
• 卷：115
• 期：31
• 页码：8682-8690
• 全文大小：1107K
• 年卷期：v.115,no.31(August 11, 2011)
• ISSN：1520-5215

文摘

For the first time, a theoretical study has been performed on the prototypical decathio[10]circulene (C₂₀S₁₀) species, which is an analogue of the novel octathio[8]circulene 鈥淪ulflower鈥?molecule (C₁₆S₈). Examinations of the singlet and triplet states of C₂₀S₁₀ were made at the B3LYP/6-311G(d) level. Local minima of C₂ and C_s symmetry were found for the lowest singlet and triplet states, respectively. The stability of C₂₀S₁₀ was assessed by calculating the 螖H掳_f of C₁₆S₈ and C₂₀S₁₀ and the 螖H^o for their decomposition into C₂S units. Frontier molecular orbital plots show that structural adjacent steric factors along with the twist and strain orientations of C₂₀S₁₀ do not disturb the aromatic 蟺-delocalizing effects. In fact, C₂₀S₁₀ maintains the same p_z HOMO character as C₁₆S₈. These similarities are further verified by density-of-states characterization. Calculated infrared spectra of C₁₆S₈ and C₂₀S₁₀ show broad similarities. Molecular electrostatic potential results reveal that eight of the peripheral sulfur atoms are the most electronegative atoms in the molecule, while the interior ten-membered ring exhibits virtually no electronegativity.