Symmetrically Tetra‐functionalized Pillar[6]arenes Prepared by Fragment Coupling

Due to the highly symmetrical structures generated from one‐pot syntheses, the partial functionalization of macrocycles is usually beset with low yields and onerous purifications of the target multifunctional macrocycles. To improve this situation, taking pillar[6]arenes as an example, a two‐step fr...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-03, Vol.61 (11), p.e202115823-n/a
Main Authors: Zeng, Hong, Liu, Peiren, Xing, Hao, Huang, Feihe
Format: Article
Language:English
Subjects:
Host–Guest Compounds
Pillararenes
Self-Assembly
Supramolecular Chemistry
Supramolecular Polymers
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Summary:Due to the highly symmetrical structures generated from one‐pot syntheses, the partial functionalization of macrocycles is usually beset with low yields and onerous purifications of the target multifunctional macrocycles. To improve this situation, taking pillar[6]arenes as an example, a two‐step fragment coupling method has been developed for synthesizing symmetrically tetra‐functionalized pillar[6]arenes, namely X‐pillar[6]arenes. This method is simple and versatile, which makes hetero‐fragment coupling and pre‐functionalization available. Nine new macrocycles and a pillar[6]arene‐based cage have been prepared. In addition, one of the newly synthesized macrocycles, COOEtEtXP[6], exhibits a strong cyan luminescence in the solid state under irradiation by 365 nm UV light. This emission originates from intramolecular through‐space conjugation. Meanwhile, formation of a supramolecular polymer by multiple non‐covalent intra/intermolecular interactions helps rigidify the structure and make COOEtEtXP[6] an efficient solid‐state emitter. It is believed that this fragment coupling can also be used to realize the multi‐functionalization of other macrocycles. A new method for synthesizing partially functionalized pillar[6]arenes is reported. It emphasizes the advantages of fragment coupling over one‐pot synthesis in terms of preparing highly modifiable macrocycles for supramolecular chemistry. Moreover, one of the synthesized pillar[6]arenes, COOEtEtXP[6], exhibits cyan luminescence due to the through‐space conjugation, which opens up new possibilities for designing luminescent macrocycles.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202115823