Study of through-space substituent–π interactions using N -phenylimide molecular balances
Study of through-space substituent–π interactions using N -phenylimide molecular balances
复制标题
使用 N-苯基酰亚胺分子平衡研究空间取代基相互作用
DOI：
10.1039/c9qo00195f
复制
发表时间：
2019
影响因子：
5.4
通讯作者：
Shimizu, Ken D.
中科院分区：
文献类型：
--
作者：
Hwang, Jungwun;Li, Ping;Vik, Erik C.;Karki, Ishwor;Shimizu, Ken D.
利用一个小的N-苯亚胺分子平衡模型体系，对取代基-π相互作用和芳香堆积相互作用进行了实验测量。在溶液中没有芳香堆积作用的情况下，测定了取代基(NH2、CH3、OH、F、Br3、CF3和NO2)与芳环的直接相互作用。测得的取代基-π能与σm参数关联良好，与芳香族堆积体系中观察到的取代基效应相似。取代基效应中的持续静电趋势可能源于取代基与相反的π-体系之间的直接静电相互作用。
Substituent–π interactions associated with aromatic stacking interactions were experimentally measured using a small N-phenylimide molecular balance model system. The direct interaction of the substituent (NH2, CH3, OH, F, Br, CF3 and NO2) with an aromatic ring was measured in the absence of the aromatic stacking interactions in solution. The measured substituent–π energies were found to correlate well with the Hammett σm parameter similar to the substituent effects observed in aromatic stacking systems. The persistent electrostatic trends in substituent effects can arise from the direct electrostatic interactions between substituents and opposing π-systems.