Three-dimensional aromaticity in an antiaromatic cyclophane
Three-dimensional aromaticity in an antiaromatic cyclophane
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DOI：
10.1038/s41467-019-11467-4
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发表时间：
2019-08-08
影响因子：
16.6
通讯作者：
Shinokubo, Hiroshi
中科院分区：
文献类型：
--
作者：
Nozawa, Ryo;Kim, Jinseok;Shinokubo, Hiroshi
了解分子间的相互作用对于阐明药物与受体的结合、蛋白质折叠和有机分子自组装的机制至关重要。虽然两个芳香族分子之间的相互作用已经被广泛研究，但对两个反芳香族分子之间的相互作用知之甚少。理论研究已经预测，反芳香分子应该是稳定的，当他们堆叠在一起，通过吸引分子间的相互作用。在这里，我们报告的合成的环蕃，其中两个反芳族卟啉部分采用堆叠的面对面的几何形状与距离短于所涉及的原子的货车范德华半径的总和。从实验和理论上研究了该环蕃的芳香性。该环蕃在两个亚基之间具有三维空间电流通道，这证实了两个反芳香π-系统之间存在相互吸引作用。
Understanding of interactions among molecules is essential to elucidate the binding of pharmaceuticals on receptors, the mechanism of protein folding and self-assembling of organic molecules. While interactions between two aromatic molecules have been examined extensively, little is known about the interactions between two antiaromatic molecules. Theoretical investigations have predicted that antiaromatic molecules should be stabilized when they stack with each other by attractive intermolecular interactions. Here, we report the synthesis of a cyclophane, in which two antiaromatic porphyrin moieties adopt a stacked face-to-face geometry with a distance shorter than the sum of the van der Waals radii of the atoms involved. The aromaticity in this cyclophane has been examined experimentally and theoretically. This cyclophane exhibits three-dimensional spatial current channels between the two subunits, which corroborates the existence of attractive interactions between two antiaromatic pi-systems.