Linear Multiselenium Interactions in Dicationic Oligomers of 1,5-(Diselena)canes: Behavior of Semc σ(mc c-ne e) (6≤mc ≤16) Elucidated with QTAIM Dual Functional Analysis.

ABSTRACT

The intrinsic dynamic and static nature mc center-ne electron interactions of the σ-type σ(mc c-ne e) were elucidated for the Se-Se interactions in dicationic oligomers of Se(CH2 CH2 CH2 )2 Se (1 (Se, Se)) [n2+ (Se, Se) n=1-8], especially for mc ≥6, where n2+ (Se, Se n=1-8) are abbreviated by n2+ (n=1-8), respectively. QTAIM dual functional analysis (QTAIM-DFA) was applied to the interactions. Perturbed structures generated using coordinates derived from the compliance constants (Cii ) were employed for QTAIM-DFA. Each Se-*-Se in 12+ and 22+ has the nature of CT-TBP (trigonal bipyramidal adduct formation through CT) and Cov-w (weak covalent), respectively, which supply the starting points of the investigations. The asterisk emphasizes the existence of a bond critical point on the interaction. All Se-*-Se in 32+ are classified by the regular closed shell (r-CS) interactions and characterized as CT-MC (molecular complex formation through CT), which are denoted as r-CS/CT-MC, except for the central interaction, of which nature is r-CS/CT-TBP. Most interactions in 42+ -82+ are r-CS/t-HBwc (typical-HB with covalency) but some are pure-CS/t-HBnc (t-HB with no covalency). The linear Se2n 2+ interactions in 22+ -82+ seem close to those without any limitations, since the nature of Se-*-Se inside and outside of (CH2 CH2 CH2 )2 are very similar with each other. The linear Se2n 2+ interactions in 32+ -82+ are shown to be analyzed as σ(mc c-ne e 6≤mc ≤16), not by the accumulated σ(3c-4e).