Dependence of the Substituent Effect on Solvent Properties

Halina Szatyłowicz , Anna Jezuita , Tomasz Siodła , Konstantin S. Varaksin , Krzysztof Ejsmont , Izabela Madura , Tadeusz Marek Krygowski

Abstract

The influence of a solvent on the substituent effect (SE) in 1,4-disubstituted derivatives of benzene (BEN), cyclohexa-1,3-diene (CHD), and bicyclo[2.2.2]octane (BCO) is studied by the use of polarizable continuum model method. In all X–R–Y systems for the functional group Y (NO2, COOH, OH, and NH2), the following substituents X have been chosen: NO2, CHO, H, OH, and NH2. The substituent effect is characterized by the charge of the substituent active region (cSAR(X)), substituent effect stabilization energy (SESE), and substituent constants σ or F descriptors, the functional groups by cSAR(Y), whereas π-electron delocalization of transmitting moieties (BEN and CHD) is characterized by a geometry-based index, harmonic oscillator model of aromaticity. All computations were carried out by means of B3LYP/6-311++G(d,p) method. An application of quantum chemistry SE models (cSAR and SESE) allows to compare the SE in water solutions and in the gas phase. Results of performed analyses indicate an enhancement of the SE by water. The obtained Hammett-type relationships document different nature of interactions between Y and X in aromatic and olefinic systems (a coexistence of resonance and inductive effects) than in saturated ones (only the inductive effect). An increase of electric permittivity clearly enhances communications between X and Y for BEN and CHD systems.
Author Halina Szatyłowicz (FC / DPC)
Halina Szatyłowicz,,
- Department Of Physical Chemistry
, Anna Jezuita
Anna Jezuita,,
-
, Tomasz Siodła
Tomasz Siodła,,
-
, Konstantin S. Varaksin
Konstantin S. Varaksin,,
-
, Krzysztof Ejsmont (FPE / IOPS)
Krzysztof Ejsmont,,
- The Institute of Organization of Production Systems
, Izabela Madura (FC / CICSST)
Izabela Madura,,
- Chair Of Inorganic Chemistry And Solid State Technology
, Tadeusz Marek Krygowski
Tadeusz Marek Krygowski,,
-
Journal seriesJournal of Physical Chemistry A, ISSN 1089-5639, (A 30 pkt)
Issue year2018
Vol122
No7
Pages1896-1904
Publication size in sheets0.5
DOIDOI:10.1021/acs.jpca.7b12023
URL https://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b12023?src=recsys
Languageen angielski
File
acs.jpca.7b12023.pdf 1.46 MB
Score (nominal)30
ScoreMinisterial score = 30.0, 24-07-2018, ArticleFromJournal
Ministerial score (2013-2016) = 30.0, 24-07-2018, ArticleFromJournal
Publication indicators WoS Impact Factor: 2016 = 2.847 (2) - 2016=2.663 (5)
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