The Nature of Transannular Interactions in E4N4 and E82+ (E = S, Se)

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• 作者：Jani Moilanen ; Antti J. Karttunen ; Heikki M. Tuononen ; Tristram Chivers
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2012
• 出版时间：November 13, 2012
• 年：2012
• 卷：8
• 期：11
• 页码：4249-4258
• 全文大小：374K
• 年卷期：v.8,no.11(November 13, 2012)
• ISSN：1549-9626

文摘

The electronic structures of tetrachalcogen tetranitrides, E₄N₄, and octachalcogen dications, E₈²⁺, and the nature of their intramolecular E路路路E interactions (E = S, Se) was studied with high-level theoretical methods. The results reveal that the singlet ground states of both systems have a surprisingly large correlation contribution which functions to weaken and therefore lengthen the cross-ring E鈥揈 bond. The observed correlation effects are primarily static in E₄N₄, whereas in E₈²⁺ the dynamic part largely governs the total correlation contribution. The presented description of bonding is the first that gives an all-inclusive picture of the origin of cross-ring interactions in E₄N₄ and E₈²⁺; not only does it succeed in reproducing all experimental structures but it also offers a solid explanation for the sporadic performance of different computational methods that has been reported in previous studies. Furthermore, the theoretical data demonstrate that E路路路E bonds in E₄N₄ and E₈²⁺ are unique and fundamentally different from, for example, dispersion that plays a major role in weak intermolecular chalcogen路路路chalcogen contacts.