title: Nature of E2X2σ(4c-6e) of the X---E-E---X type at naphthalene 1,8-positions and model, elucidated by X-ray crystallographic analysis and QC calculations with the QTAIM approach.
abstract: The nature of E2X2σ(4c-6e) of the X-*-E-*-E-*-X type is elucidated for 1-(8-XC10H6)E-E(C10H6X-8')-1' [(1) E, X = S, Cl; (2) S, Br; (3) Se, Cl; (4) Se, Br] after structural determination of (1), (3) and (4), together with model A [MeX---E(H)-E(H)---XMe (E = S and Se; X = Cl and Br)]. The quantum theory of atoms-in-molecules dual functional analysis (QTAIM-DFA) is applied. The total electron energy densities Hb(rc) are plotted versus Hb(rc) - Vb(rc)/2 for the interactions at the bond critical points (BCPs; *), where Vb(rc) show the potential energy densities at the BCPs. Data for the perturbed structures around the fully optimized structures are employed for the plots, in addition to those of the fully optimized structures. The plots were analysed using the polar coordinate (R, θ) representation of the data of the fully optimized structures. Data containing the perturbed structures were analysed by (θp, κp), where θpcorresponds to the tangent line of the plot and κpis the curvature. Whereas (R, θ) shows the static nature, (θp, κp) represents the dynamic nature of interactions. E-*-E are all classified as shared shell (S) interactions for (1)-(4) and as weak covalent (Cov-w) in nature (S/Cov-w). The nature of pure CS (closed shell)/typical-HB (hydrogen bond) with no covalency is predicted for E-*-X in (1) and (3), regular CS/typical-HB nature with covalency is predicted for (4), and an intermediate nature is predicted for (2). The NBO energies evaluated for E-*-X in (1)-(4) are substantially larger than those in model A due the shortened length at the naphthalene 1,8-positions. The nature of E2X2of σ(4c-6e) is well elucidated via QTAIM-DFA.
authors.affiliation: Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University, 930 Sakaedani, Wakayama 640-8510, Japan.
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Tsubomoto
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: Waro
authors.initials: W
authors.lastname: Nakanishi
authors.affiliation: Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Takahiro
authors.initials: T
authors.lastname: Sasamori
authors.affiliation: Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Norihiro
authors.initials: N
authors.lastname: Tokitoh
keywords: ab initio calculations; extended hypervalent interactions; halogen bonds; hydrogen-bond nature; quantum theory of atoms-in-molecules (QTAIM)