relation: http://publicatio.bibl.u-szeged.hu/29671/
title: Cooperative Self-Assembly in Linear Chains Based on Halogen Bonds
creator:  Vermeeren Pascal
creator:  Wolters Lando P.
creator:  Paragi Gábor
creator:  Fonseca Guerra Celia
subject: 01.03. Fizikai tudományok
description: 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-C6H4-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 sigma-electronic system by charge-transfer between the lone-pair orbital of the nitrogen (sigma(HOMO)) on one unit and the acceptor orbital of the C-X (sigma*(LUMO)) on the adjacent unit. As such, the HOMO-LUMO gap in the sigma-system decreases, and the cooperativity increases with chain length revealing the similarity in the bonding mechanisms of hydrogen and halogen bonds.
date: 2021
type: Folyóiratcikk
type: PeerReviewed
format: text
identifier: http://publicatio.bibl.u-szeged.hu/29671/2/ChemPlusChem202186812-fulltext.pdf
identifier:     Vermeeren Pascal;  Wolters Lando P.;  Paragi Gábor;  Fonseca Guerra Celia: Cooperative Self-Assembly in Linear Chains Based on Halogen Bonds.   CHEMPLUSCHEM, 86 (6).  pp. 812-819.  ISSN 2192-6506 (2021)     
identifier: doi:10.1002/cplu.202100093
relation: https://doi.org/10.1002/cplu.202100093
relation: 32049042
language: eng