Desymmetrized Leaning Pillar[6]arene
Desymmetrized Leaning Pillar[6]arene
复制标题
去对称斜柱[6]芳烃
DOI：
10.1002/anie.201805980
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发表时间：
2018-07-26
影响因子：
16.6
通讯作者：
Yang, Ying-Wei
中科院分区：
文献类型：
--
作者：
Wu, Jia-Rui;Mu, Anthony U.;Yang, Ying-Wei
在这项工作中，发现了一种新型的大环芳烃，即倾斜柱[6]芳烃，它可以被认为是去除了两个羟基/烷氧基官能团的柱[6]芳烃的倾斜版本。通过简单的两步合成方法，结合多种后修饰可能性，合成了一系列具有良好空腔适应性和增强的客体结合能力的倾斜柱[6]芳烃，并呈现出它们在单晶状态下的自组装。 DFT计算表明，未取代亚苯基环较低的旋转势垒、以倾斜苯环为中心的不均匀电子密度以及氢键诱导的羟基取向产生的沿边缘的极化效应极大地影响了主客体性质，同时为传统柱[6]芳烃的柱状刚性结构提供了直观的解释。值得注意的是，环低聚醌的晶体结构是通过倾斜柱[6]芳烃的直接氧化获得的。
In this work, a novel version of macrocyclic arenes, namely leaning pillar[6]arenes, was discovered and it can be considered as a tilted version of a pillar[6]arene with two hydroxy/alkoxy functionalities removed. Through a facile two-step synthetic approaches, in conjunction with a diversity of post-modification possibilities, a series of leaning pillar[6]arenes, with good cavity adaptability and enhanced guest-binding capability, was synthesized, and their self-assembly in single-crystal states is presented. DFT calculations demonstrated that the lower rotational barrier of unsubstituted phenylene rings, the uneven electron density centered at the leaning phenyl rings, and the polarization effect along the edge generated by the hydrogen-bond-induced orientation of hydroxy groups greatly affected the host-guest properties, and meanwhile provided an intuitive explanation for the pillar-like and rigid structure of traditional pillar[6]arenes. Significantly, the crystal structure of cyclo-oligomeric quinone was obtained by direct oxidation of leaning pillar[6]arenes.