title: Hydroxyl group as a substituent with varying electronic properties: effect of strength of H-bonding on charge density changes in Ph-OH…F⁻ complexes.
abstract: Due to gradual and controlled changes of interatomic distances between heavy atoms in OH…F⁻ of C(6)H(5)OH…F⁻ systems it was possible to study the electronic structure evolution. Computation at B3LYP/6-311+G(d,p) level of theory was performed for this purpose. Changes in charges at atoms and characteristics at bond critical points (BCPs) of the H-bond region and also in distant parts of the systems were investigated by means of natural bond orbitals (NBO) and atoms in molecules (AIM) analyses. It is shown that at the border line between partially covalent and non-covalent H-bonding (Espinosa et al. in J Chem Phys 117:5529, 2002; Grabowski et al. in J Phys Chem B 110:6444, 2006) with the H…F interatomic distance ~1.8 Ǻ the hydrogen atom has the most positive charge. In addition, the change in the atomic charge values in the interacting region affects the phenyl ring properties. The decrease of the sum of atomic charges as well as of the aromaticity was noticed when the OH….F distance is shortened.
authors.affiliation: Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland. halina@ch.pw.edu.pl
authors.forename: Halina
authors.initials: H
authors.lastname: Szatyłowicz
authors.forename: Tadeusz Marek
authors.initials: TM
authors.lastname: Krygowski
authors.forename: Aneta
authors.initials: A
authors.lastname: Jezierska-Mazzarello
mesh_terms: D004581:Electronics; D005459:Fluorides / Q000737:chemistry; D006860:Hydrogen Bonding; D006878:Hydroxides / Q000737:chemistry*; D019800:Phenol / Q000737:chemistry*; D055672:Static Electricity
chemical_list: D006878:Hydroxides; D019800:Phenol; C031356:hydroxide ion; D005459:Fluorides
references.citation: J Org Chem. 2005 Oct 28;70(22):8859-65
references.pmid: 16238319
references.citation: J Chem Inf Model. 2007 May-Jun;47(3):875-86
references.pmid: 17444628
references.citation: J Org Chem. 2004 Oct 15;69(21):7038-43
references.pmid: 15471450
references.citation: J Phys Chem A. 2006 Jun 8;110(22):7232-6
references.pmid: 16737274
references.citation: Chemistry. 2007;13(28):7996-8006
references.pmid: 17607686
references.citation: Chem Rev. 2005 Oct;105(10):3513-60
references.pmid: 16218560
references.citation: J Phys Chem B. 2006 Apr 6;110(13):6444-6
references.pmid: 16570938
references.citation: Annu Rev Phys Chem. 1997;48:511-44
references.pmid: 9348662
references.citation: Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
references.pmid: 9944570
references.citation: J Phys Chem A. 2005 Jul 28;109(29):6532-9
references.pmid: 16833999
references.citation: Chem Rev. 2005 Oct;105(10):3482-512
references.pmid: 16218559