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.

Organic emitters with persistent phosphorescence have shown potential application in optoelectronic devices. However, rational design and phosphorescence tuning are still challenging. Here, a series of metal-free luminophores without heavy atoms and carbonyl groups from commercial/lab-synthesized carbazole and benzene were synthesized to realize tunable molecular emission from fluorescence to phosphorescence by simply substituent variation. All the molecules emit blue fluorescence in both solution and solid state. Upon removal of excitation source, the fluorinated luminophores show obvious phosphorescence. The labsynthesized carbazole based molecules exhibit a huge lifetime difference to the commercially purchased ones due to the existence of isomer in the latter samples. The small energy gap between singlet and triplet state and low reorganization energy help enhance intersystem crossing to contribute to a more competitive radiative process from triplet to ground state. Blue and white organic light-emitting devices are fabricated by using fluorinated luminophore as emitting layer.

Photodynamic therapy (PDT) is a promising noninvasive therapeutic technique and has attracted increasing interests in preclinical trials. However, the translation from laboratory to clinic often encounters the problem of undesired dark cytotoxicity of photosensitizers (PSs). Now, this challenge can be addressed by cascaded substitution activated phototheranostics using the host–guest strategy. Through electrostatical complexation of pyridinium-functionalized tetraphenylethylene, namely, TPE-PHO, and water-soluble calixarene, the dark cytotoxicity of TPE-PHO is dramatically inhibited. The nanoassemblies of the complex show enhanced biocompatibility and selectively locate at the cytoplasm in vitro. When TPE-PHO is competitively displaced from the cavity of calixarene by 4,4′-benzidine dihydrochloride at the tumor site, its dark cytotoxicity and photoactivity in tumor tissue are restored to give efficient PDT efficacy under light irradiation. The result from cell imaging reveals that TPE-PHO undergoes translocation from cytoplasm to mitochondria to kill the cancer cells during the cascaded supramolecular substitution process. In vivo tumor imaging and therapy are successfully implemented to evaluate the curative effect. Such a supramolecular strategy avoids tedious molecular synthesis and opens a new venue to readily tune the PS behaviors.

White-light emissive materials with stable photophysical properties are of great importance for their potential applications in information display, fluorescent sensors, and optical-recording systems. Herein, an amphiphilic tetraphenylpyrazine (TPP)-based cage compound (TPP-Cage) was facilely synthesized by reaction of propeller-like TPP with aggregation-induced emission characteristics and triglycol monomethyl ether-substituted triazine. By immobilizing the twisted conformation of TPP, TPP-Cage showed obvious helical chirality in the solution and aggregated state. TPP-Cage emits strong deep blue fluorescence in solution due to the restriction of intramolecular rotation of the TPP unit. Its amphiphilic nature enables it to serve as an excellent lightharvesting platform to encapsulate diketopyrrolopyrrole (DPP) with aggregation-caused quenching effect in its hydrophobic cavity in aqueous medium, forming the DPP@ TPP-Cage complex. Such inclusion prevents π−π stacking of DPP enabling it to emit strong yellow-light emission in the aggregated state. Due to the complementary emission colors of TPP-Cage and DPP, DPP@TPP-Cage exhibited stable white-light emission in the aggregated state and poly(ethylene glycol) film. This work not only introduces a promising strategy for development of chiral compounds through immobilization of propellerlike achiral molecules but also provides a prospective pathway for white-light emission based on supramolecular assembly.

This review highlights the recent development of chiral materials with aggregation-induced emission properties, including their molecular structures, self-assembly and functions.

The discovery of the photophysical phenomenon of aggregation-induced emission (AIE) by Tang in 2001 has drawn intense attention of scientists all over the world and created potential applications in various areas, such as biological probes, chemical sensors, and optoelectronic devices. Incorporation of AIE with chirality is a pioneering attempt to broaden the field of AIE research. Generally, chiral AIEgens are designed by attaching chiral units to an AIE-active building block. From another point of view, AIEgens with molecular rotors or vibrators are a kind of latent chiral molecule, whose chirality can be detected at a specific state by breaking the mirror symmetry. Aggregation as a bridge tethers molecular AIEgens and their macroscopic self-assembly. Through precise control of the chirality, well-defined helical architectures with amplified chiral signals are formed. In contrast to circularly-polarized luminescence at the molecular level, these aggregates with ordered packing always show enhanced performance in emission efficiency and dissymmetry factor.

ICT-type AIEgens with twisted conformations are ideal candidates for high-contrast mechanochromic luminogens under external force.

Enantioselective recognition and separation have attracted much attention in pharmaceutical analysis, food chemistry, and life science. Herein, we propose an efficient strategy to achieve such purposes using optically active luminogens with aggregation-induced emission (AIE) characteristics. These AIE luminogens (AIEgens) show strong enantiomeric discrimination for 12 kinds of chiral acids and unprotected amino acids. In particular, an exceptionally high enantioselectivity for d/l-Boc-glutamic acid was observed, as demonstrated by the large difference between the formed AIEgen/acid complexes. Due to the AIE effect, enantioselective separation was achieved by aggregation of the AIEgens with one enantiomer in the mixed acid solution. Through analysis of the fluorescence standard curve, the aggregates of AIEgen/chiral acid possessed 90% d-analyte, from which the enantiomeric excess (ee) value was assessed to be 80% ee. Such a result is in good agreement with that (91% d-analyte and 82% ee) by chiral HPLC analysis. Thus, this simple one-step aggregation method can serve as a preliminary screening tool for high-throughput analysis or separation of chiral chemicals.