Pillar[5]arenes: fascinating cyclophanes with a bright future

• Published in: Chemical Society reviews 2012-01, Vol.41 (2), p.597-607
• Main Authors: Cragg, Peter J, Sharma, Kushal
• Format: Article
• Language: English
• Subjects: Calixarenes - chemistry; Crystallography, X-Ray; Ethers, Cyclic - chemistry; Macrocyclic Compounds - chemistry; Molecular Conformation; Quaternary Ammonium Compounds - chemical synthesis; Quaternary Ammonium Compounds - chemistry
• ISSN: 0306-0012; 1460-4744
• DOI: 10.1039/c1cs15164a

Pillar[5]arenes are [1(5)]paracyclophane derivatives consisting of 1,4-disubstituted hydroquinones linked by methylene bridges in the 2,5-positions. The first report of these novel macrocycles was in 2008, when 1,4-dimethoxypillar[5]arene was prepared in 22% yield, and subsequent improvements in synthetic methods have allowed the number of derivatives to expand significantly. In addition to D(5) symmetric pillar[5]arenes, asymmetric pillar[5]arenes with two different substituents in the 1- and 4-positions and copillar[5]arenes consisting of two different repeat units in a 4 : 1 ratio have been synthesised. Crystallographic, computational and spectroscopic studies are starting to shed light on the compounds' unusual inclusion phenomena, from gelation and transportation of water through nanotubes to the formation of chromogenic rotaxanes. Applications as molecular sensors are starting to appear with a focus on guest detection by fluorescence quenching. This tutorial review will provide a summary of research into the pillar[5]arenes since their recent discovery.