Stacking Interactions: A Supramolecular Approach to Upgrade Weak Halogen Bond Donors

Stacking Interactions: A Supramolecular Approach to Upgrade Weak Halogen Bond Donors

Bibliographic Details
Parent link:Chemistry - A European Journal
Vol. 28, iss. 70.— 2022.— [e202201869, 10 p.]
Corporate Author: Национальный исследовательский Томский политехнический университет Исследовательская школа химических и биомедицинских технологий (ИШХБМТ)
Other Authors: Baykov S. V. Sergey Valentinovich, Ivanov D. M. Daniil Mikhaylovich, Kasatkina S. O. Svetlana Olegovna, Galmes B. Bartomeu, Frontera A. Antonio, Resnati D. P. Dzhuzeppe Paolo, Kukushkin A. Yu. Vadim Yurjevich
Summary: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
Language:English
Published: 2022
Subjects:
труды учёных ТПУ
электронный ресурс
crystal engineering
DFT calculations
halogen bonding
noncovalent interactions
staking
кристаллотехника
галогенные связи
нековалентные взаимодействия
Online Access:https://doi.org/10.1002/chem.202201869
Format: Electronic Book Chapter
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=379357

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