Faculty of Chemistry, Nicolaus Copernicus University in Toruń, Gagarina 7, 87-100 Toruń, Poland.
Molecules. 2023 Feb 28;28(5):2244. doi: 10.3390/molecules28052244.
The forms of molecular iron maidens are known for their unique ultrashort interaction between the apical hydrogen atom or its small substituent and the surface of the benzene ring. It is generally believed that this forced ultrashort X⋯π contact is associated with high steric hindrance, which is responsible for specific properties of iron maiden molecules. The main aim of this article is to investigate the influence of significant charge enrichment or depletion of the benzene ring on the characteristics of the ultrashort C-X⋯π contact in iron maiden molecules. For this purpose, three strongly electron-donating (-NH2) or strongly electron-withdrawing (-CN) groups were inserted into the benzene ring of -[34,10][7]metacyclophane and its halogenated (X = F, Cl, Br) derivatives. It is shown that, despite such extremely electron-donating or electron-accepting properties, the considered iron maiden molecules surprisingly reveal quite high resistance to changes in electronic properties.
分子铁娘子的形式以其独特的超短氢键或其小取代基与苯环表面之间的相互作用而闻名。一般认为，这种强制的超短 X⋯π 接触与高空间位阻有关，这是铁娘子分子具有特定性质的原因。本文的主要目的是研究苯环上显著的电荷富集或耗尽对铁娘子分子中超短 C-X⋯π 接触特性的影响。为此，将三个强给电子（-NH2）或强吸电子（-CN）基团插入到 -[34,10][7]metacyclophane 及其卤代（X = F、Cl、Br）衍生物的苯环中。结果表明，尽管具有如此极端的供电子或吸电子性质，但所考虑的铁娘子分子出人意料地显示出对电子性质变化的相当高的抵抗力。
