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The Two Faces of Hydrogen‐Bond Strength on Triple AAA–DDD Arrays
Author(s) -
Lopez Alfredo Henrique Duarte,
Caramori Giovanni Finoto,
Coimbra Daniel Fernando,
Parreira Renato Luis Tame,
da Silva Éder Henrique
Publication year - 2013
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.201300639
Subject(s) - natural bond orbital , chemistry , atoms in molecules , hydrogen bond , electron localization function , intermolecular force , supramolecular chemistry , covalent bond , triple bond , crystallography , molecule , bond order , three center two electron bond , computational chemistry , non covalent interactions , chemical physics , bond length , electron , density functional theory , double bond , crystal structure , organic chemistry , physics , quantum mechanics
Systems that are connected through multiple hydrogen bonds are the cornerstone of molecular recognition processes in biology, and they are increasingly being employed in supramolecular chemistry, specifically in molecular self‐assembly processes. For this reason, the effects of different substituents (NO 2 , CN, F, Cl, Br, OCH 3 and NH 2 ) on the electronic structure, and consequently on the magnitude of hydrogen bonds in triple AAA–DDD arrays (A=acceptor, D=donor) were evaluated in the light of topological [electron localization function (ELF) and quantum theory of atoms in molecules (QTAIM)], energetic [Su–Li energy‐decomposition analysis (EDA) and natural bond orbital analysis (NBO)], and geometrical analysis. The results based on local H‐bond descriptors (geometries, QTAIM, ELF, and NBO) indicate that substitutions with electron‐withdrawing groups on the AAA module tend to strengthen, whereas electron‐donating substituents tend to weaken the covalent character of the AAA–DDD intermolecular H‐bonds, and also indicate that the magnitude of the effect is dependent on the position of substitution. In contrast, Su–Li EDA results show an opposite behavior when compared to local H‐bond descriptors, indicating that electron‐donating substituents tend to increase the magnitude of H‐bonds in AAA–DDD arrays, and thus suggesting that the use of local H‐bond descriptors describes the nature of H bonds only partially, not providing enough insight about the strength of such H bonds.