title: Transannular E···E' Interactions in Neutral, Radical Cationic, and Dicationic Forms of cyclo-[E(CH2CH2CH2)2E'] (E, E' = S, Se, Te, and O) with Structural Feature: Dynamic and Static Behavior of E···E' Elucidated by QTAIM Dual Functional Analysis.
abstract: The nature of the transannular E-∗-E' interactions in neutral, radical cationic, and dicationic forms of cyclo-E(CH2CH2CH2)2E' (1) (E, E' = S, Se, Te, and O) (1, 1(•+), and 1(2+), respectively) is elucidated by applying QTAIM dual functional analysis (QTAIM-DFA). Hb(rc) are plotted versus Hb(rc) - Vb(rc)/2 for the data of E-∗-E' at BCPs in QTAIM-DFA, where ∗ emphasizes the existence of BCP. Plots for the fully optimized structures are analyzed by the polar coordinate (R, θ) representation. Those containing the perturbed structures are by (θp, κp): θp corresponds to the tangent line of the plot, and κp is the curvature. While (R, θ) describes the static nature, (θp, κp) represents the dynamic nature of interactions. The nature is well-specified by (R, θ) and (θp, κp). E-∗-E' becomes stronger in the order of 1 < 1(•+) < 1(2+), except for O-∗-O. While E-∗-E' (E, E' = S, Se, and Te) in 1(2+) are characterized as weak covalent bonds, except for S-∗-Te (MC nature through CT) and Se-∗-Te (TBP nature through CT), O-∗-E' seems more complex. The behavior of E-∗-E' in 1(2+) is very close to that of cyclo-E(CH2CH2CH2)E' (E, E' = S, Se, Te, and O), except for O-∗-O.
authors.affiliation: Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University , 930 Sakaedani, Wakayama 640-8510, Japan.
authors.forename: Satoko
authors.initials: S
authors.lastname: Hayashi
authors.affiliation: Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University , 930 Sakaedani, Wakayama 640-8510, Japan.
authors.forename: Kohei
authors.initials: K
authors.lastname: Matsuiwa
authors.affiliation: Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University , 930 Sakaedani, Wakayama 640-8510, Japan.
authors.forename: Nozomu
authors.initials: N
authors.lastname: Nishizawa
authors.affiliation: Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University , 930 Sakaedani, Wakayama 640-8510, Japan.
authors.forename: Waro
authors.initials: W
authors.lastname: Nakanishi