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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| Main Authors: | |
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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 |
| Summary: | 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. |
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| Physical Description: | 812-819 |
| ISSN: | 2192-6506 |