Substituent Effect and Its Halogen-Atom Dependence of Halogen Bonding Viewed through Electron Density Changes
Substituent Effect and Its Halogen-Atom Dependence of Halogen Bonding Viewed through Electron Density Changes
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从电子密度变化观察卤素键的取代基效应及其卤素原子依赖性
DOI：
10.1002/asia.202201196
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Torii Hajime
中科院分区：
文献类型：
--
作者：
Sakai Takanori;Torii Hajime
阐明卤素键合能力和强度如何通过取代基效应控制以及这种控制如何依赖于卤素原子对于功能重要分子的微调设计至关重要。在这里，通过分析不同取代的卤代苯的电子密度差异/变化来解决这个问题。结果表明，卤素原子周围电子分布的各向异性是决定卤素成键能力的重要因素，它受取代基效应的影响不大，而是简单地取决于卤素原子，而与C−X键的键偶极子相关的卤素原子上的部分电荷受到取代基效应的显着调制，导致C−X键延伸线上的静电势增强。还讨论了与偏振效应相关的特性。
Elucidating how the halogen‐bonding ability and strength are controlled by the substituent effect and how this control depends on halogen atom will be essential for finely‐tuned design of functionally important molecules. Here, this problem is tackled by analyzing the electron density differences/changes for variously substituted halobenzenes. It is shown that the anisotropy of the electron distribution around the halogen atom, which is an important factor for halogen‐bonding ability, is not much affected by the substituent effect and rather simply depends on the halogen atom, while the partial charge on the halogen atom, which is related to the bond dipole of the C−X bond, is significantly modulated by the substituent effect and gives rise to enhancement of the electrostatic potential on the line extended from the C−X bond. The properties related to the polarization effect are also discussed.