Abstract
© 2021 The Authors. ChemPlusChem published by Wiley-VCH GmbHCooperative 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 σ-electronic system by charge-transfer between the lone-pair orbital of the nitrogen (σHOMO) on one unit and the acceptor orbital of the C−X (σ*LUMO) on the adjacent unit. As such, the HOMO-LUMO gap in the σ-system decreases, and the cooperativity increases with chain length revealing the similarity in the bonding mechanisms of hydrogen and halogen bonds.
Original language | English |
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Pages (from-to) | 812-819 |
Journal | ChemPlusChem |
Volume | 86 |
Issue number | 6 |
DOIs | |
Publication status | Published - 1 Apr 2021 |
Funding
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 7 European Community Framework Programme. th 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.
Funders | Funder number |
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Dutch Astrochemistry Network | |
Netherlands Organization for Scientific Research NWO | |
Seventh Framework Programme |