Molecular aggregates are self-assembled from multiple molecules via weak intermolecular interactions, and new chemical and physical properties can emerge compared to their individual molecule. With the development of aggregate science, much research has focused on the study of the luminescence behaviour of aggregates rather than single molecules. Pyrene as a classical fluorophore has attracted great attention due to its diverse luminescence behavior depending on the solution state, molecular packing pattern as well as morphology, resulting in wide potential applications. For example, pyrene prefers to emit monomer emission in dilute solution but tends to form a dimer via π–π stacking in the aggregation state, resulting in red-shifted emission with quenched fluorescence and quantum yield. Over the past two decades, much effort has been devoted to developing novel pyrene-based fluorescent molecules and determining the luminescence mechanism for potential applications. Since the concept of “aggregation-induced emission (AIE)” was proposed by Tang et al. in 2001, aggregate science has been established, and the aggregated luminescence behaviour of pyrene-based materials has been extensively investigated. New pyrene-based emitters have been designed and synthesized not only to investigate the relationships between the molecular structure and properties and advanced applications but also to examine the effect of the aggregate morphology on their optical and electronic properties. Indeed, new aggregated pyrene-based molecules have emerged with unique properties, such as circularly polarized luminescence, excellent fluorescence and phosphorescence and electroluminescence, ultra-high mobility, etc. These properties are independent of their molecular constituents and allow for a number of cutting-edge technological applications, such as chemosensors, organic light-emitting diodes, organic field effect transistors, organic solar cells, Li-batteries, etc. Reviews published to-date have mainly concentrated on summarizing the molecular design and multi-functional applications of pyrene-based fluorophores, whereas the aggregation behaviour of pyrene-based luminescent materials has received very little attention. The majority of the multi-functional applications of pyrene molecules are not only closely related to their molecular structures, but also to the packing model they adopt in the aggregated state. In this review, we will summarize the intriguing optoelectronic properties of pyrene-based luminescent materials boosted by aggregation behaviour, and systematically establish the relationship between the molecular structure, aggregation states, and optoelectronic properties. This review will provide a new perspective for understanding the luminescence and electronic transition mechanism of pyrene-based materials and will facilitate further development of pyrene chemistry.

“Unity is force” – Aesop. It is a common phenomenon that traditional chromophores exhibit high fluorescence in dilute solutions, yet luminescence is quenched at high concentrations or in the aggregate state, i.e. “aggregation-caused quenching” (ACQ). Tang reported the unusual photophysical observation that luminogens can exhibit weak or no fluorescence in solution, yet they are highly emissive in the aggregate or solid state; this is defined as aggregation-induced emission (AIE). The discovery of AIE helped solve the ACQ effect in traditional luminophores. Pyrene is an important polycyclic aromatic hydrocarbon (PAH), which exhibits very different photophysical behavior in solution versus the aggregate state, and the ACQ effect has played a dominant role in pyrene chemistry. The ACQ effect is harmful for some practical applications and is a challenge in organic light-emitting diodes (OLEDs) and light-emitting electrochemical cells, for which the effect is more severe in the solid state. Thus, how to overcome the ACQ effect observed in pyrene chemistry still remains a challenge. In this review, we discuss how following basic AIE mechanisms such as the restriction of intramolecular motion (RIM), excited-state intramolecular proton transfer (ESIPT), and twisted intramolecular charge transfer (TICT), can transform pyrene-based ACQ luminogens to AIE luminogens with excellent optical properties. Furthermore, prospective applications of pyrene-based AIEgens are discussed, as is the potential for designing new organic functional materials.

Lipid droplets are highly associated with obesity, diabetes, inflammatory disorders and cancer. A reliable two-photon dye for specific lipid droplets imaging in live cells and live tissues at ultra-low concentration has rarely been reported. In this work, four new aggregation-induced emission luminogens (AIEgens) based on the naphthalene core were designed and synthesized for specific two-photon lipid droplets staining. The new molecules, namely NAP AIEgens, exhibit large Stokes shift (>110 nm), high solid-state fluorescence quantum yield (up to 30%), good two-photon absorption cross section (45–100 GM at 860 nm), high biocompatibility and good photostability. They could specifically stain lipid droplets at ultra-low concentration (50 nM) in a short time of 15 min. Such ultra-low concentration is the lowest value for lipid droplets staining in live cells reported so far. In vitro and ex vivo two-photon imaging of lipid droplets in live cells and live mice liver tissues were successfully demonstrated. In addition, selective visualization of lipid droplets in live mice liver tissues could be achieved at a depth of about 70 μm. These excellent properties render them as promising candidates for investigating lipid droplets-associated physiological and pathological processes in live biological samples.

This article presents a new strategy to achieve white-light emission from single tetraphenylethylene-substituted pyrenes (TPE-Pys) with aggregation-induced emission (AIE) characteristics. TPE-Pys were synthesized by a Pd-catalyzed coupling reaction of a boronic acid or pinacol ester of pyrene and tetraphenylethylene (TPE) derivatives and showed multicolor emission by introducing different substituents on the phenyl rings of TPE. TPE-Pys with a TPE unit at the 1-position and asymmetric TPE units at 2,7-positions show dual fluorescence in THF/water mixtures to realize white-light emission with CIE coordinates of (x = 0.30 and y = 0.41) and (x = 0.21 and y = 0.16), respectively. The structure–property relationship of TPE-Pys were investigated to elucidate the origin of the white emission. The results showed that due to the weak electronic interaction of pyrene and its chromophoric units at the 2,7-positions and the constraint of the rotation of the TPE unit at the 1-position of pyrene, each component can exhibit its own emission color. The combination of appropriate colors gives rise to white-light emission. Such a principle of molecular design may open a new avenue for preparing advanced multicolor and multifunctional optical materials for organic electronics.