Cooperative Self-Assembly in Linear Chains Based on Halogen Bonds.

ABSTRACT: Cooperative properties of halogen bonds were investigated with computational experiments based on dispersion-corrected relativistic density functional theory. The bonding mechanism in linear chains of cyanogen halide (X-CN), halocyanoacetylene (X-CC-CN), and 4-halobenzonitrile (X-C₆ H₄ -CN) were examined for X = H, Cl, Br, and I. Our energy decomposition and Kohn-Sham molecular-orbital analyses revealed the bonding mechanism of the studied systems. Cyanogen halide and halocyanoacetylene chains possess an extra stabilizing effect with increasing chain size, whereas the 4-halobenzonitrile chains do not. This cooperativity can be traced back to charge separation within the σ-electronic system by charge-transfer between the lone-pair orbital of the nitrogen (σ_HOMO

SUBMITTER: Vermeeren P 

PROVIDER: S-EPMC8252609 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature