A through-space description of substituent effects leads to inaccurate molecular electrostatic potentials and cation⋯π interactions in extended aromatic systems

2016 ◽  
Vol 18 (20) ◽  
pp. 13750-13753 ◽  
Author(s):  
Enrique M. Cabaleiro-Lago ◽  
Jesús Rodríguez-Otero
Keyword(s):  
Substituent Effects ◽  
Electrostatic Potentials ◽  
Molecular Electrostatic Potentials ◽  
Space Model ◽  
Effect Of Substituents ◽  
Π Interactions ◽  
Aromatic Systems ◽  
Space Description

The effect of substituents in extended aromatic systems spreads to the whole molecule. Predictions based on the currently accepted through-space model give significant deviations on the strength of cation⋯π interactions.

Study of the molecular electrostatic potentials of zeolites: the acidity in offretite

1988 ◽  
Vol 92 (15) ◽  
pp. 4456-4461 ◽  
Author(s):  
A. Goursot ◽  
F. Fajula ◽  
C. Daul ◽  
J. Weber
Keyword(s):  
Electrostatic Potentials ◽  
Molecular Electrostatic Potentials

Anomalous stabilizing and destabilizing effects in some cyclic π-electron systems

1993 ◽  
Vol 71 (8) ◽  
pp. 1123-1127 ◽  
Author(s):  
Peter Politzer ◽  
M. Edward Grice ◽  
Jane S. Murray ◽  
Jorge M. Seminario
Keyword(s):  
Ab Initio ◽  
Lone Pair ◽  
Electrostatic Potentials ◽  
Electron Delocalization ◽  
Isodesmic Reaction ◽  
Computational Studies ◽  
Electron Systems ◽  
Molecular Electrostatic Potentials ◽  
Lone Pairs

Ab initio computational studies have been carried out for three molecules that are commonly classed as antiaromatic: cyclobutadiene (1), 1,3-diazacyclobutadiene (7), and 1,4-dihydropyrazine (6). Their dinitro and diamino derivatives were also investigated. Stabilizing or destabilizing energetic effects were quantified by means of the isodesmic reaction procedure at the MP2/6-31G*//HF/3-21G level, and calculated molecular electrostatic potentials (HF/STO-5G//HF/3-21G) were used as a probe of electron delocalization. Our results do not show extensive delocalization in the π systems of any one of the three parent molecules. The destabilization found for 1 and 7 is attributed primarily to strain and to repulsion between the localized π electrons in the C=C and C=N bonds, respectively. However, 6 is significantly stabilized, presumably due to limited delocalization of the nitrogen lone pairs. NH2 groups are highly stabilizing, apparently because of lone pair delocalization. NO2 is neither uniformly stabilizing nor destabilizing.

Intermolecular binding preferences of haloethynyl halogen-bond donors as a function of molecular electrostatic potentials in a family of N-(pyridin-2-yl)amides

2021 ◽  
Author(s):  
Amila M. Abeysekera ◽  
Boris B. Averkiev ◽  
Pierre Le Magueres ◽  
Christer B. Aakeröy
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Halogen Bond ◽  
Electrostatic Potentials ◽  
Halogen Bonds ◽  
Molecular Electrostatic Potentials

The roles played by halogen bonds and hydrogen bonds in the crystal structures of N-(pyridin-2-yl)amides were evaluated and rationalised in the context of calculated molecular electrostatic potentials.

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