title: The Nature of Transannular Interactions in E4N4 and E8(2+) (E = S, Se).
abstract: The electronic structures of tetrachalcogen tetranitrides, E4N4, and octachalcogen dications, E8(2+), and the nature of their intramolecular E···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-E bond. The observed correlation effects are primarily static in E4N4, whereas in E8(2+) 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 E8(2+); 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···E bonds in E4N4 and E8(2+) are unique and fundamentally different from, for example, dispersion that plays a major role in weak intermolecular chalcogen···chalcogen contacts.
authors.affiliation: Department of Chemistry, P.O. Box 35, FI-40014 University of Jyväskylä, Finland.
authors.forename: Jani
authors.initials: J
authors.lastname: Moilanen
authors.affiliation: Department of Chemistry, P.O. Box 35, FI-40014 University of Jyväskylä, Finland.
authors.forename: Antti J
authors.initials: AJ
authors.lastname: Karttunen
authors.affiliation: Department of Chemistry, P.O. Box 35, FI-40014 University of Jyväskylä, Finland.
authors.forename: Heikki M
authors.initials: HM
authors.lastname: Tuononen
authors.affiliation: Department of Chemistry, University of Calgary, Calgary, AB, T2N 1N4, Canada.
authors.forename: Tristram
authors.initials: T
authors.lastname: Chivers