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

Autor: Baykov SV; Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg, 199034, Russian Federation.; Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Tomsk, 634034, Russian Federation., Ivanov DM; Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg, 199034, Russian Federation.; Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Tomsk, 634034, Russian Federation., Kasatkina SO; Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg, 199034, Russian Federation., Galmés B; Departament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122, Palma de Mallorca, Baleares, Spain., Frontera A; Departament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122, Palma de Mallorca, Baleares, Spain., Resnati G; Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Tomsk, 634034, Russian Federation.; NFMLab, Department of Chemistry, Materials, Chemical Engineering, 'Giulio Natta Politecnico di Milano', via Mancinelli 7, I-20131, Milano, Italy., Kukushkin VY; Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg, 199034, Russian Federation.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2022 Dec 15; Vol. 28 (70), pp. e202201869. Date of Electronic Publication: 2022 Nov 10.
DOI: 10.1002/chem.202201869
Abstrakt: The co-crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co-crystals TCB ⋅ ArX (ArX=PhCl, PhBr, 4-MeC 6 H 4 Cl, 4-MeC 6 H 4 Br, 4-MeOC 6 H 4 Cl, 1,2-Br 2 C 6 H 4 ) 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⋅⋅⋅N cyano 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-MeOC 6 H 4 Cl (featuring an electron-rich arene moiety and exhibiting very poor σ-hole-(Cl) ability) increases significantly in the stacked trimer (TCB) 2  ⋅ 4-MeOC 6 H 4 Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋅⋅⋅N cyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes.
(© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje