Calixarenes, Macrocycles with (Almost) Unlimited Possibilities

TLDR

Calixarenes are cyclic oligomers of phenol units formed by a one‑step condensation of p‑tert‑butylphenol or resorcinol with aldehydes, yielding tetramers, hexamers, or octamers that can serve as highly specific ligands, sensors, decontamination agents, artificial enzymes, and building blocks for advanced materials such as nonlinear optics and ultrathin sieve membranes. The parent compounds can be modified at phenolic hydroxy groups or phenyl residues, allowing separate or combined functionalization. The condensation proceeds without dilution, enabling large‑scale production, and calixarenes serve as versatile starting materials for host molecules and as building blocks for larger, functionally defined molecular systems.

Abstract

Abstract The condensation reaction between p‐tert ‐butylphenol and formaldehyde leads in a single step to good yields of cyclic oligomers in which, depending on the reaction conditions, either four, six, or eight phenol units are joined by methylene bridges. The beakerlike shape of the most stable conformation of the tetramer has led to their being given the name “calixarenes” (calix = chalice). Resorcinol can undergo condensation in a similar manner with a variety of aldehydes to afford cyclic tetramers with the same basic structure (the resorcarenes). In both cases the reaction does not require the use of dilution techniques, so that large quantities of product can be readily obtained. In addition, the parent compounds can be modified in various ways, in particular at the phenolic hydroxy groups or the phenyl residues; these approaches can be used separately or in combination. Calixarenes are thus ideal starting materials for the synthesis of various types of host molecules and can also act as building blocks for the construction of larger molecular systems with defined structures and functions. Their potential applications range from use as highly specific ligands for analytical chemistry, sensor techniques and medical diagnostics to their use in the decontamination of waste water and the construction of artificial enzymes and the synthesis of new materials for non‐linear optics or for ultrathin layers and sieve membranes with molecular pores.