Supramolecular‐Macrocycle‐Based Crystalline Organic Materials

Abstract Supramolecular macrocycles are well known as guest receptors in supramolecular chemistry, especially host−guest chemistry. In addition to their wide applications in host−guest chemistry and related areas, macrocycles have also been employed to construct crystalline organic materials (COMs) owing to their particular structures that combine both rigidity and adaptivity. There are two main types of supramolecular‐macrocycle‐based COMs: those constructed from macrocycles themselves and those prepared from macrocycles with other organic linkers. This review summarizes recent developments in supramolecular‐macrocycle‐based COMs, which are categorized by various types of macrocycles, including cyclodextrins, calixarenes, resorcinarenes, pyrogalloarenes, cucurbiturils, pillararenes, and others. Effort is made to focus on the structures of supramolecular‐macrocycle‐based COMs and their structure–function relationships. In addition, the application of supramolecular‐macrocycle‐based COMs in gas storage or separation, molecular separation, solid‐state electrolytes, proton conduction, iodine capture, water or environmental treatment, etc., are also presented. Finally, perspectives and future challenges in the field of supramolecular‐macrocycle‐based COMs are discussed.