Condensation of 1,4-dimethoxybenzene (DMB) with paraformaldehyde in the presence of BF3.O(C2H5)2 gave novel para-bridged pentacyclic pillar DMB (DMpillar[5]arene). Moreover, para-bridged pentacyclic hydroquinone (pillar[5]arene) was prepared. Pillar[5]arene formed 1:1 host-guest complexes with dialkyl viologen and alkyl pyridinium derivatives. However, pillar[5]arene did not form complexes with the diadamantyl viologen derivative since a bulky adamantyl group was unable to thread the cavity of pillar[5]arene.

In 2008, we reported a new class of pillar-shaped macrocyclic hosts, known as "pillar[n]arenes". Today, pillar[n]arenes are recognized as key players in supramolecular chemistry because of their facile synthesis, unique pillar shape, versatile functionality, interesting host-guest properties, and original supramolecular assembly characteristics, which have resulted in numerous electrochemical and biomedical material applications. In this Review, we have provided historical background to macrocyclic chemistry, followed by a detailed discussion of the fundamental properties of pillar[n]arenes, including their synthesis, structure, and host-guest properties. Furthermore, we have discussed the applications of pillar[n]arenes to materials science, as well as their applications in supramolecular chemistry, in terms of their fundamental properties. Finally, we have described the future perspectives of pillar[n]arene chemistry. We hope that this Review will provide a useful reference for researchers working in the field and inspire discoveries concerning pillar[n]arene chemistry.

Water-soluble pillar[5]arene was synthesized by the introduction of carboxylate anions at both upper and lower rims. When cationic viologen salt was mixed with the water-soluble pillar[5]arene in aqueous media, a very stable 1:1 host-guest complex was formed.

The rotation behavior of the phenolic units in pillar [5]arenes has been studied by means of the dynamic 1 H NMR measurements. In acetone-d 6 , the individual conformers of pillar[5]arene were observed under -60 °C, indicating that the rotation movement was slow on the NMR time scale under -60 °C. In permethylated pillar[5]arene in acetone-d 6 , the peaks were not split even at -90 °C, strongly suggesting that the rotation movement was fast on the NMR time scale at -90 °C. This is due to the lack of the intramolecular hydrogen bond belt in permethylated pillar[5]arene. In the mixture of pillar[5]arene and viologen guest in acetone-d 6 , the split peaks were found at -30 °C and did not change under -60 °C. By formation of the host-guest complex between pillar[5]arene and viologen guest, the rotation movement was slow on the NMR time scale under -30 °C and almost stopped under -60 °C.

A series of pillar[5]arene derivatives with alkyl groups of different length were synthesized. The new alkyl-substituted pillar[5]arene derivatives 1,4-bis(ethoxy)pillar[5]arene (C2), 1,4-bis(propoxy)pillar[5]arene (C3), 1,4-bis(butoxy)pillar[5]arene (C4), 1,4-bis(pentyloxy)pillar[5]arene (C5), 1,4-bis(hexyloxy)pillar[5]arene (C6), and 1,4-bis(dodecanoxy)pillar[5]arene (C12) were obtained by Lewis acid-catalyzed condensation of dialkoxybenzene monomers with paraformaldehyde. The conformational characteristics of the pillar[5]arene derivatives were investigated by dynamic (1)H NMR measurements. When the alkyl substituents were bulkier than methyl groups, the rotation of phenolic units in the pillar[5]arenes was suppressed and their conformation was immobilized. As their length increased, the alkyl substituents packed at the upper and lower rims and thus lowered the conformational freedom of the pillar[5]arenes.