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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Quantitative assessment of substituent effects on cation-π interactions using molecular electrostatic potential topography
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Quantitative assessment of substituent effects on cation-π interactions using molecular electrostatic potential topography

机译：使用分子静电势形貌定量评估取代基对阳离子-π相互作用的影响

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摘要

A molecular electrostatic potential (MESP) topography based approach has been proposed to quantify the substituent effects on cation-π interactions in complexes of mono-, di-, tri-, and hexasubstituted benzenes with Li ~+, Na~+, K~+, and NH_4~+. The MESP minimum (V_(min)) on the π-region of C_6H _5X showed strong linear dependency to the cation-π interaction energy, E_(M+). Further, cation-π distance correlated well with V_(min)-π distance. The difference between V_(min) of C _6H_5X and C_6H_6 (ΔV _(min)) is proposed as a good parameter to quantify the substituent effect on cation-π interaction. Compared to benzene, electron-donating groups stabilize the di-, tri-, and hexasubstituted cation-π complexes while electron-withdrawing groups destabilize them. In multiple substituted complexes, E_(M+) is almost equal (～95%) to the sum of the individual substituent contributions (E_(M+) ≈ Σ(ΔE_(M+))), suggesting that substituent effect on cation-π interactions is largely additive. The ΔV_(min) of C_6H_5X systems and additivity feature have been used to make predictions on the interaction energies of 80 multiple substituted cation-π complexes with above 97% accuracy. The average mean absolute deviation of the V_(min)-predicted interaction energy, E_(M+)~V from the calculated E _(M+) is -0.18 kcal/mol for Li~+, -0.09 kcal/mol for Na ~+, -0.43 kcal/mol for K~+, and -0.67 kcal/mol for NH _4~+, which emphasize the predictive power of V _(min) as well as the additive feature of the substituent effect.
机译：已经提出了一种基于分子静电势（MESP）拓扑的方法来量化取代基对单取代，二取代，三取代和六取代的苯与Li〜+，Na〜+，K〜+的络合物中阳离子-π相互作用的影响。和NH_4〜+。 C_6H _5X的π区域上的MESP最小值（V_（min））对阳离子-π相互作用能E_（M +）具有很强的线性依赖性。此外，阳离子-π距离与V_（min）-π距离很好地相关。提出了C _6H_5X的V_（min）和C_6H_6之间的差（ΔV_（min））作为量化取代基对阳离子-π相互作用的良好参数。与苯相比，给电子基团稳定了二，三和六取代的阳离子-π络合物，而吸电子基团则使它们不稳定。在多个取代的配合物中，E_（M +）几乎等于各个取代基贡献的总和（E_（M +）≈Σ（ΔE_（M +））），表明取代基对阳离子-π相互作用的影响为主要是累加的。 C_6H_5X系统的ΔV_（min）和可加性特征已用于对80种多重取代的阳离子-π配合物的相互作用能进行预测，其准确度高于97％。 V_（min）预测的相互作用能E_（M +）〜V与计算得出的E _（M +）的平均平均绝对偏差（对于Li〜+为-0.18 kcal / mol，对于Na〜+为-0.09 kcal / mol） ，K〜+为-0.43 kcal / mol，NH _4〜+为-0.67 kcal / mol，这突出了V_（min）的预测能力以及取代基效应的累加特征。

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