Cooperative Self-Assembly in Linear Chains Based on Halogen Bonds
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 exami...
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| Format: | Article |
| Published: |
2021
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| Series: | CHEMPLUSCHEM
86 No. 6 |
| Subjects: | |
| doi: | 10.1002/cplu.202100093 |
| mtmt: | 32049042 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/29671 |
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| 245 | 1 | 0 | |a Cooperative Self-Assembly in Linear Chains Based on Halogen Bonds |h [elektronikus dokumentum] / |c Vermeeren Pascal |
| 260 | |c 2021 | ||
| 300 | |a 812-819 | ||
| 490 | 0 | |a CHEMPLUSCHEM |v 86 No. 6 | |
| 520 | 3 | |a 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. | |
| 650 | 4 | |a Fizikai tudományok | |
| 700 | 0 | 1 | |a Wolters Lando P. |e aut |
| 700 | 0 | 1 | |a Paragi Gábor |e aut |
| 700 | 0 | 1 | |a Fonseca Guerra Celia |e aut |
| 856 | 4 | 0 | |u http://publicatio.bibl.u-szeged.hu/29671/2/ChemPlusChem202186812-fulltext.pdf |z Dokumentum-elérés |