par Berger, Gilles 
;Soubhye, Jalal ;Van Der Lee, Arie;Vande Velde, Christophe ;Wintjens, René ;Dubois, Philippe;Clement, Sébastien ;Meyer, Franck
Référence ChemPlusChem, 79, 4, page (552-558)
Publication Publié, 2014
;Soubhye, Jalal ;Van Der Lee, Arie;Vande Velde, Christophe ;Wintjens, René ;Dubois, Philippe;Clement, Sébastien ;Meyer, Franck Référence ChemPlusChem, 79, 4, page (552-558)
Publication Publié, 2014
Article révisé par les pairs
| Résumé : | The supramolecular organization of modified thiophenes resulting from N⋯I halogen bonding (XB) has been studied. X-ray diffraction analyses of two polymorphs of the same supramolecular complex showed an arrangement controlled by halogen-bonded pyridyl and tetrafluoroiodobenzene rings, one case with and the other without the presence of two different lone pair (lp)⋯π interactions, namely O⋯pyridyl and I⋯ tetrafluoroiodobenzene contacts. To shed light on the interplay between these interactions, quantum mechanical calculations were performed at the ωB97X-D/6-31+G(d,p) level on both systems in the gas phase. The longer N⋯I distance observed in the crystal structure without lp⋯π interactions was also corroborated by dispersion-corrected DFT. These results represent the first case in which a synergy between lp⋯π interactions and XB is observed experimentally and confirmed by calculations. Getting organized: X-ray diffraction analyses of two polymorphs of a supramolecular thiophene complex show an arrangement controlled by N⋯I halogen bonding (XB), one case with and the other without the presence of two different lone pair (lp)⋯π interactions, namely O⋯pyridyl and I⋯tetrafluoroiodobenzene contacts (see figure). Quantum mechanical calculations confirm the interplay between concomitant XB and lp⋯π interactions. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
