Stacking Interactions: A Supramolecular Approach to Upgrade Weak Halogen Bond Donors; Chemistry - A European Journal; Vol. 28, iss. 70
| Parent link: | Chemistry - A European Journal Vol. 28, iss. 70.— 2022.— [e202201869, 10 p.] |
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| Collectivité auteur: | |
| Autres auteurs: | , , , , , , |
| Résumé: | Title screen The co-crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co-crystals TCB ⋅ ArX (ArX=PhCl, PhBr, 4-MeC6H4Cl, 4-MeC6H4Br, 4-MeOC6H4Cl, 1,2-Br2C6H4) which were studied by X-ray diffraction. In these systems, the strong collective effect of π⋅⋅⋅π stacking interactions and lone pair-(X)⋅⋅⋅π-hole-(C) bondings between TCB and ArX promote the strength of X⋅⋅⋅Ncyano halogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the σ-hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the σ- hole-(Cl) value (1.5 kcal/mol) in the haloarene 4-MeOC6H4Cl (featuring an electron-rich arene moiety and exhibiting very poor σ-hole-(Cl) ability) increases significantly in the stacked trimer (TCB)2 ⋅ 4-MeOC6H4Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋅⋅⋅Ncyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes. Режим доступа: по договору с организацией-держателем ресурса |
| Langue: | anglais |
| Publié: |
2022
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| Sujets: | |
| Accès en ligne: | https://doi.org/10.1002/chem.202201869 |
| Format: | Électronique Chapitre de livre |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=379357 |
| Résumé: | Title screen The co-crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co-crystals TCB ⋅ ArX (ArX=PhCl, PhBr, 4-MeC6H4Cl, 4-MeC6H4Br, 4-MeOC6H4Cl, 1,2-Br2C6H4) which were studied by X-ray diffraction. In these systems, the strong collective effect of π⋅⋅⋅π stacking interactions and lone pair-(X)⋅⋅⋅π-hole-(C) bondings between TCB and ArX promote the strength of X⋅⋅⋅Ncyano halogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the σ-hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the σ- hole-(Cl) value (1.5 kcal/mol) in the haloarene 4-MeOC6H4Cl (featuring an electron-rich arene moiety and exhibiting very poor σ-hole-(Cl) ability) increases significantly in the stacked trimer (TCB)2 ⋅ 4-MeOC6H4Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋅⋅⋅Ncyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes. Режим доступа: по договору с организацией-держателем ресурса |
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| DOI: | 10.1002/chem.202201869 |