%0 Journal Article
%@ 2192-6506
%A  Vermeeren Pascal
%A  Wolters Lando P.
%A  Paragi Gábor
%A  Fonseca Guerra Celia
%A MTA-SZTE Biomimetikus Rendszerek Kutatócsoport SZTE / SZAOK / OVI [2017-2022],
%A Fizikai Intézet PTE / TTK FI,
%D 2021
%F publicatio:29671
%J CHEMPLUSCHEM
%N 6
%P 812-819
%T Cooperative Self-Assembly in Linear Chains Based on Halogen Bonds
%U http://publicatio.bibl.u-szeged.hu/29671/
%V 86
%X 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.
%Z Funding Agency and Grant Number: Netherlands Organization for Scientific Research NWO (ECHO); Dutch Astrochemistry Network (DAN); Marie Curie Intra European Fellowship within the 7th European Community Framework Programme             Funding text: We gratefully acknowledge the financial support from the Netherlands Organization for Scientific Research NWO (ECHO), Dutch Astrochemistry Network (DAN), and the Marie Curie Intra European Fellowship within the 7th European Community Framework Programme.