Liu Yuezhou, Wang Hongliang, Liu Peiren, Zhu Huangtianzhi, Shi Bingbing, Hong Xin, Huang Feihe
State Key Laboratory of Chemical Engineering, Center for Chemistry of High-Performance & Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027, P. R. China.
Department of Chemistry, Zhejiang University, Hangzhou, 310058, China.
Angew Chem Int Ed Engl. 2021 Mar 8;60(11):5766-5770. doi: 10.1002/anie.202015597. Epub 2021 Jan 26.
Azobenzene (azo)-based macrocycles are highly fascinating in supramolecular chemistry because of their light-responsiveness. In this work, a series of azo-based macrocyclic arenes 1, 2, 3, and 4, distinguished by the substituted positions of azo groups, is rationally designed and synthesized via a fragment-cyclization method. From the crystal and computed structures of 1, 2, and 3, we observe that the cavity size of these azo-macrocycles decreases gradually upon E→Z photoisomerization. Moreover, light-controlled host-guest complexations between azo-macrocycle 1 and guest molecules (7,7,8,8-tetracyanoquinodimethane, terephthalonitrile) are successfully achieved. This work provides a simple and effective method to prepare azo-macrocycles, and the light-responsive molecular-encapsulation systems in this work may further advance the design and applications of novel photo-responsive host-guest systems.
基于偶氮苯的大环化合物因其光响应性在超分子化学中极具吸引力。在这项工作中，通过片段环化方法合理设计并合成了一系列基于偶氮苯的大环芳烃1、2、3和4，它们通过偶氮基团的取代位置加以区分。从1、2和3的晶体结构及计算结构中，我们观察到这些偶氮大环化合物的空腔尺寸在E→Z光异构化时会逐渐减小。此外，成功实现了偶氮大环化合物1与客体分子（7,7,8,8 - 四氰基对苯二醌二甲烷、对苯二甲腈）之间的光控主客体络合。这项工作提供了一种制备偶氮大环化合物的简单有效方法，并且本工作中的光响应分子封装系统可能会进一步推动新型光响应主客体系统的设计与应用。
