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The Role of Molecular Electrostatic Potentials in the Formation of a Halogen Bond in Furan⋅⋅⋅XY and Thiophene⋅⋅⋅XY Complexes
Author(s) -
Zeng Yanli,
Zhang Xueying,
Li Xiaoyan,
Meng Lingpeng,
Zheng Shijun
Publication year - 2011
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201100008
Subject(s) - halogen bond , thiophene , furan , halogen , atoms in molecules , chemistry , non covalent interactions , atom (system on chip) , electrostatics , interaction energy , molecule , crystallography , computational chemistry , hydrogen bond , organic chemistry , alkyl , computer science , embedded system
Abstract The halogen bonding of furan⋅⋅⋅XY and thiophene⋅⋅⋅XY (X=Cl, Br; Y=F, Cl, Br), involving σ‐ and π‐type interactions, was studied by using MP2 calculations and quantum theory of “atoms in molecules” (QTAIM) studies. The negative electrostatic potentials of furan and thiophene, as well as the most positive electrostatic potential ( V S,max ) on the surface of the interacting X atom determined the geometries of the complexes. Linear relationships were found between interaction energy and V S,max of the X atom, indicating that electrostatic interactions play an important role in these halogen‐bonding interactions. The halogen‐bonding interactions in furan⋅⋅⋅XY and thiophene⋅⋅⋅XY are weak, “closed‐shell” noncovalent interactions. The linear relationship of topological properties, energy properties, and the integration of interatomic surfaces versus V S,max of atom X demonstrate the importance of the positive σ hole, as reflected by the computed V S,max of atom X, in determining the topological properties of the halogen bonds.