1,8-Dioxyanthracene-based bisarylene crown ethers, composed of ethylene glycol chains and aromatic moieties, have been synthesized. Complexation studies revealed that these crown ethers could form 1:1 complexes with methyl viologen dication (N,N′-dimethyl-4,4′-bipyridinium dication; MV²⁺) in a mixed solvent of CDCl₃ and CD₃CN (1:1 v/v) with association constants in a range of (1.2 ± 0.1) × 10³ M^–1 to (1.6 ± 0.2) × 10⁴ M^–1. The structure of the complex and the strength of the π-donor/π-acceptor interactions between the 1,8-dioxyanthracene planes and the pyridinium rings of MV²⁺ are highly dependent on the length of the polyether chains of the ethers. Structural analysis showed that the tetraethylene glycol-derived bis-1,8-dioxyanthracene-based crown ether 9 forms a U-shaped host-guest complex with MV²⁺ by inserting the coplanar pyridinium rings of MV²⁺ between the two parallel oriented 1,8-dioxyanthracene units of 9, which is driven predominantly by π-donor/π-acceptor interactions. The pentaethylene glycol-derived bis-1,8-dioxyanthracene-based crown ether 10, however, adopts a crescent-shaped conformation in complex 10⊃MV²⁺ with the MV²⁺ guest being encapsulated by the polyether chains, propelled mainly by the hydrogen-bonding interactions between the hydrogen atoms of MV²⁺ and the oxygen atoms of the polyether chains of 10. Similarly, the hexaethylene glycol-derived bis-1,8-dioxyanthracene-based crown ether 11 forms a complex with MV²⁺. However, only weak π-donor/π-acceptor interactions between the aromatic groups of the mixed bisarylene crown ethers 12 and 13, and MV²⁺ were observed, and construction of tetracationic cyclophane [CBPQT⁴⁺] and crown ether 13 based [2]catenane 15 was achieved through supramolecular interactions between the [CBPQT⁴⁺] ring and naphtho unit in the crown ether.

Tetraamido-oxacalix[4]arene derivatives have been synthesized via the reactions of tetraamino-oxacalix[4]arene with excess butyryl chloride, octanoyl chloride, benzoyl chloride and p-toluenesulfonyl chloride, respectively. ¹H NMR results suggest that these oxacalix[4]arene derivatives preferentially adopt the 1,3-alternate (saddle-like) conformation in solution, which were also the case in the solid state as demonstrated by single crystal X-ray analysis. A dimerized slipped capsule could be formed by tetra-butyramido-oxacalix[4]arene in the solid state via intermolecular hydrogen bond interactions under the assistance of two encapsulated methanol molecules. On the other hand, a molecular cavity was formed by tetra-p-toluenesulfonamido-oxacalix[4]arene which can encapsulate a solvent molecule of ethyl acetate.

Oxacalix[4]aromatics comprised of terphenylene units have been synthesized by cyclooligomerization of 5′-tert-butyl-1,1′:3′,1″-terphenyl-4,4″-diol (1) and electron-deficient meta-dihalogenated benzene and heterocycles. Single-crystal X-ray analysis revealed that oxacalix[2]terphenylene[2]pyrazine 13 adopts a chair conformation, forming a molecular cavity to trap an ethyl acetate guest molecule in the solid state. 1,3-Alternate conformations are adopted by other oxacalix[2]terphenylene[2]aromatics (11, 12 and 15), which form a narrow tweezer-like molecular cavity that is incapable of encapsulating any guest molecules.