The Designs and Applications of Tetraphenylethylene Macrocycles and Cages

Abstract Macrocycles and cages are very attractive for the development of functional materials due to their unique inner cavities. Building blocks with interesting functions and synthetic conveniences are especially attractive. Tetraphenylethylene (TPE) is such an entity with C 2 symmetry and tetrakis ‐functional groups easily modifiable. As a typical aggregation‐induced emission (AIE) active compound, TPE perfectly unites the functions of fluorescence and structural building blocks together. The unique marriage of the two roles into one component makes TPE an ideal platform for the development of functional molecular systems including macrocycles and cages. The TPE macrocycles and cages are not merely a simple combination of those two but also generate added values unseen in either component alone. The fluorescence properties of TPE in macrocycles/cages are greatly improved or modulated, which makes them more suitable for various applications compared to their linear counterparts. In this review, the chemistry and design principles of TPE macrocycles/cages are surveyed first. The unique properties of those compounds are also discussed to provide general guidance for their functionalization. A brief discussion of their applications focusing on the utilization of their unique fluorescence is also presented. In the last, outlooks and future perspectives of TPE macrocycles/cages are provided for further developments.