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@ARTICLE{Kol:201319,
author = {Kolář, Michal and Hostaš, Jiří and Hobza, Pavel},
title = {{T}he strength and directionality of a halogen bond are
co-determined by the magnitude and size of the σ-hole},
journal = {Physical chemistry, chemical physics},
volume = {16},
number = {21},
issn = {1463-9084},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2015-03624},
pages = {9987 -},
year = {2014},
abstract = {The σ-holes of halogen atoms on various aromatic scaffolds
were described in terms of their size and magnitude. The
electrostatic potential maps at the
CAM-B3LYP-D3(bj)/def2-QZVP level were calculated and the
σ-holes of more than 100 aromatic analogues were thoroughly
analysed to relate the σ-holes to the binding preferences
of the halogenated compounds. Both the size and magnitude of
the σ-hole increase when passing from chlorinated to
iodinated analogues. Also, the σ-hole properties were
studied upon chemical substitution of the aromatic ring as
well as in the aromatic ring. Further, the angular
variations of the interactions were investigated on a
selected set of halogenbenzene complexes with argon and
hydrogen fluoride (HF). In order to analyse interaction
energy components, DFT-SAPT angular scans were performed.
The interaction energies of bromobenzene complexes were
evaluated at the CCSD(T)/complete basis set level providing
the benchmark energetic data. The strength of the halogen
bond between halogenbenzenes and Ar atoms and HF molecules
increases while its directionality decreases when passing
from chlorine to iodine. The decrease of the directionality
of the halogen bond is larger for a HF-containing complex
and is caused by electrostatic and exchange-repulsion
energies. These findings are especially valuable for
protein-halogenated ligand-binding studies, applied in the
realm of rational drug development and lead optimisation.},
cin = {GRS / IAS-5},
ddc = {540},
cid = {I:(DE-Juel1)GRS-20100316 / I:(DE-Juel1)IAS-5-20120330},
pnm = {899 - ohne Topic (POF2-899)},
pid = {G:(DE-HGF)POF2-899},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000335924800026},
pubmed = {24477636},
doi = {10.1039/c3cp55188a},
url = {https://juser.fz-juelich.de/record/201319},
}