Organic molecules with an aggregation-induced emission (AIE) effect have recently been attracting more and more attention due to their colossal potential in solid emitters and chemo/biosensors. The number and variety of AIEgen compounds are expanding very rapidly to obtain better application performance and a wider area of application. Among AIEgen systems, tetraphenylethylene (TPE) and its derivatives are the class that have received the most extensive study and the most rapid development because of their facile synthesis. Due to its C2 symmetry and at least tetratopic reaction positions, the TPE unit is also an ideal building block for constructing macrocycles and cages. The resultant cyclic TPE compounds have exhibited many exceptional performances that are difficult to access in their open chain counterparts, such as AIE enhancement, improvement in selectivity and sensitivity as sensors, emission tuning by guests, supramolecular catalysis, further disclosure of the AIE mechanism, molecular adsorption, storage and release, the propeller-like conformation exploitation of the TPE unit in chiral materials and so on. Recently, therefore, a large variety of studies about the synthesis, properties and application research of TPE macrocycles and cages have been reported. These TPE macrocycles and cages significantly expand the research area for the AIE phenomenon and its applications, and represent a development of the AIE area. However, up to now, no review of TPE macrocycles and cages has been available. Thus, this review serves as a summary of the designs, synthesis, photophysical properties, self-assembly, applications and prospects of TPE macrocycles and cages.
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