Szatylowicz Halina, Jezuita Anna, Siodła Tomasz, Varaksin Konstantin S, Ejsmont Krzysztof, Madura Izabela D, Krygowski Tadeusz M
Faculty of Chemistry, Warsaw University of Technology , Noakowskiego 3, 00-664 Warsaw, Poland.
Faculty of Chemistry, Opole University , Oleska 48, 45-052 Opole, Poland.
J Phys Chem A. 2018 Feb 22;122(7):1896-1904. doi: 10.1021/acs.jpca.7b12023. Epub 2018 Feb 8.
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 (NO, COOH, OH, and NH), the following substituents X have been chosen: NO, CHO, H, OH, and NH. 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.
采用极化连续介质模型方法研究了溶剂对苯（BEN）、环己-1,3-二烯（CHD）和双环[2.2.2]辛烷（BCO）的1,4-二取代衍生物中取代基效应（SE）的影响。对于官能团Y（NO、COOH、OH和NH）的所有X-R-Y体系，选择了以下取代基X：NO、CHO、H、OH和NH。取代基效应通过取代基活性区域的电荷（cSAR(X)）、取代基效应稳定能（SESE）和取代基常数σ或F描述符来表征，官能团通过cSAR(Y)来表征，而传递部分（BEN和CHD）的π电子离域则通过基于几何的指数——芳香性的谐振子模型来表征。所有计算均采用B3LYP/6-311++G(d,p)方法进行。量子化学SE模型（cSAR和SESE）的应用使得能够比较水溶液和气相中的SE。所进行的分析结果表明水增强了SE。所得到的哈米特型关系证明了芳香族和烯烃体系中Y与X之间相互作用的性质（共振和诱导效应并存）与饱和体系中（仅诱导效应）不同。介电常数的增加明显增强了BEN和CHD体系中X与Y之间的相互作用。
