Tipping the Balance between S-π and O-π Interactions
Tipping the Balance between S-π and O-π Interactions
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DOI：
10.1021/jacs.8b07617
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发表时间：
2018-10-17
影响因子：
15
通讯作者：
Shimizu, Ken D.
中科院分区：
文献类型：
--
作者：
Hwang, Jungwun;Li, Ping;Shimizu, Ken D.
一个全面的实验调查，包括36个分子的平衡进行比较18对S-PI与O-PI的相互作用在广泛的结构，几何和溶剂参数。在整个平衡对库中的硫和氧平衡的折叠能之间观察到强烈的线性相关性。更稳定的相互作用系统地从O-π相互作用切换到S-π相互作用。双分子PhSCH 3-芳烃和PhOCH 3-芳烃复合物的计算研究能够复制的分子平衡的实验趋势。O-pi到S-pi相互作用的偏好变化是由于稳定（分散和疏溶剂）和不稳定（交换排斥）项的相互作用，这些项是由氧原子和硫原子的大小和极化率的差异引起的。
A comprehensive experimental survey consisting of 36 molecular balances was conducted to compare 18 pairs of S-pi versus O-pi interactions over a wide range of structural, geometric, and solvent parameters. A strong linear correlation was observed between the folding energies of the sulfur and oxygen balances across the entire library of balance pairs. The more stable interaction systematically switched from the O-pi to S-pi interaction. Computational studies of bimolecular PhSCH3-arene and PhOCH3-arene complexes were able to replicate the experimental trends in the molecular balances. The change in preference for the O-pi to S-pi interaction was due to the interplay of stabilizing (dispersion and solvophobic) and destabilizing (exchange-repulsion) terms arising from the differences in size and polarizability of the oxygen and sulfur atoms.