title: Tuning of chalcogen bonds by cation-π interactions: cooperative and diminutive effects.
abstract: The tunability of Y···N chalcogen bond via formation of a cation-π interaction in ternary complexes M(+)-PhYH-NH3, M(+)-PhYH-NCH, and M(+)-PhCCCN-YHF (M = Li, Na; Y = Se, Te) is investigated at MP2/aug-cc-pVDZ computational level. Our results indicate that the strength of Y···N and cation-π interactions in the ternary complexes depends on the role of the aromatic molecule. That is, a cooperative effect is evident if aromatic molecule acts as the Lewis acid and Lewis base, simultaneously, while a diminutive effect is observed when the aromatic molecule acts only as the Lewis base in both Y···N and cation-π interactions. For a given aromatic system, the shortening or lengthening of Y···N distances is more important for Li(+) complexes than Na(+) counterparts. The mechanism of cooperative/diminutive effects in the ternary complexes is studied by molecular electrostatic potential (MEP) and topological analysis of the electron density.
authors.affiliation: Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, Maragheh, 5513864596, Iran. esrafili@maragheh.ac.ir.
authors.forename: Mehdi D
authors.initials: MD
authors.lastname: Esrafili
authors.affiliation: Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, Maragheh, 5513864596, Iran.
authors.forename: Nasibeh
authors.initials: N
authors.lastname: Saeidi
authors.affiliation: Department of Chemistry, Faculty of Sciences, Arak University, Arak, 38156-8-8349, Iran.
authors.forename: Mohammad
authors.initials: M
authors.lastname: Solimannejad
mesh_terms: D002412:Cations / Q000737:chemistry*; D018011:Chalcogens / Q000737:chemistry*; D006860:Hydrogen Bonding; D058116:Lewis Acids / Q000737:chemistry; D058115:Lewis Bases / Q000737:chemistry; D008958:Models, Molecular; D011789:Quantum Theory
chemical_list: D002412:Cations; D018011:Chalcogens; D058116:Lewis Acids; D058115:Lewis Bases
keywords: AIM; Cation-π; Chalcogen bond; ELF; MEP; Tunability