Macrocycles consisting of naphthalene units connected via methylene bridges offer certain advantages as macrocylic scaffolds as compared with parent calixarenes. These advantages originate from their electron rich and enlarged cavities. Additionally, macrocycles containing 1,3-bridged naphthalene units are dissymmetric and therefore they present interesting stereochemical features, including inherent chirality. We describe here a facile, one-step synthesis of two new calix[4]naphthalenes, by the condensation of 1,6-dimethoxynaphthalene with formaldehyde catalyzed by Brønsted acid (TFA). Additionally, we show the first example of hybrid[n]arene containing a 1,6-dimethoxynaphthalene unit and 1,3-dimethoxybenzene units obtained by a simple, one-pot condensation. The conformational and complexation properties were also studied for the resulting hybrid macrocycles.

The solid state structures of four complexes between para-sulphonato-calix[4]arene and phenanthroline have been determined. Three are simple complexes between the two molecules however the fourth contains aluminium cations, from a solid state extraction involving aluminium foil used in the weighing step. The phenanthroline cations are involved both in inclusion and also in various assemblies formed by aromatic–aromatic stacking.

The following work presents three general approaches allowing for the first time the synthesis of 5,10-diheterotruxene derivatives containing two identical heteroatoms, namely oxygen OOC, nitrogen NNC or sulfur SSC. Two of described pathways involve the photocyclisation of the corresponding triene 2 as a key step leading to heptacyclic aromatic system. The third approach is based on the acidic condensation between ninhydrin 14 and benzo[b]heteroole 15. Typical functionalizations of 5,10-diheterotruxene core have been also presented. In addition, the article discusses the advantages and limitations of the three suggested paths for receiving specific 5,10-diheterotruxene derivatives, because the universal method suitable for obtaining molecules with any type of heteroatoms is not known so far.