Recent Advances in the Synthesis and Applications of Nitrogen-Containing Macrocyclic Arenes

Macrocyclic arenes are rich-electron macrocycles bridged by methylene or methyl groups from aromatic rings substituted by hydroxyl or alkoxy groups. It has attracted great interest in host–guest chemistry and supramolecular self-assembly due to its clear cavity, adjustable structure and multifunctional binding ability. In particular, nitrogen-containing macrocyclic arenes including (hetero) aromatic moieties—constructed from building blocks such as pyrrole, carbazole, phenothiazine, and imidazole—have undergone rapid development, yielding a new generation of functional macrocycles, including calix[4]carbazoles, Tröger’s base-derived macrocycles, and phenothiazine-based architectures. These nitrogen-functionalized macrocycles feature rich chemical derivatization potential, unique structural and host–guest characteristics, and exceptional photophysical properties. They show great promise in molecular recognition, selective adsorption and separation, and the development of advanced functional materials. This review summarizes recent advances in the design, synthesis, and application of nitrogen-containing macrocyclic arenes, with a particular focus on structure–property relationships and emerging functions.