High‐Performance Quinoline‐Malononitrile Core as a Building Block for the Diversity‐Oriented Synthesis of AIEgens

In vivo fluorescent monitoring of physiological processes with high‐fidelity is essential in disease diagnosis and biological research, but faces extreme challenges due to aggregation‐caused quenching (ACQ) and short‐wavelength fluorescence. The development of high‐performance and long‐wavelength aggregation‐induced emission (AIE) fluorophores is in high demand for precise optical bioimaging. The chromophore quinoline‐malononitrile (QM) has recently emerged as a new class of AIE building block that possesses several notable features, such as red to near‐infrared (NIR) emission, high brightness, marked photostability, and good biocompatibility. In this minireview, we summarize some recent advances of our established AIE building block of QM, focusing on the AIE mechanism, regulation of emission wavelength and morphology, the facile scale‐up and fast preparation for AIE nanoparticles, as well as potential biomedical imaging applications.     

Far‐Red and Near‐IR AIE‐Active Fluorescent Organic Nanoprobes with Enhanced Tumor‐Targeting Efficacy: Shape‐Specific Effects

The rational design of high‐performance fluorescent materials for cancer targeting in vivo is still challenging. A unique molecular design strategy is presented that involves tailoring aggregation‐induced emission (AIE)‐active organic molecules to realize preferable far‐red and NIR fluorescence, well‐controlled morphology (from rod‐like to spherical), and also tumor‐targeted bioimaging. The shape‐tailored organic quinoline–malononitrile (QM) nanoprobes are biocompatible and highly desirable for cell‐tracking applications. Impressively, the spherical shape of QM‐5 nanoaggregates exhibits excellent tumor‐targeted bioimaging performance after intravenously injection into mice, but not the rod‐like aggregates of QM‐2.     

Recent Advances in Aggregation-Induced Emission Active Materials for Sensing of Biologically Important Molecules and Drug Delivery System

The emergence and development of aggregation induced emission (AIE) have attracted worldwide attention due to its unique photophysical phenomenon and for removing the obstacle of aggregation-caused quenching (ACQ) which is the most detrimental process thereby making AIE an important and promising aspect in various fields of fluorescent material, sensing, bioimaging, optoelectronics, drug delivery system, and theranostics. In this review, we have discussed insights and explored recent advances that are being made in AIE active materials and their application in sensing, biological cell imaging, and drug delivery systems, and, furthermore, we explored AIE active fluorescent material as a building block in supramolecular chemistry. Herein, we focus on various AIE active molecules such as tetraphenylethylene, AIE-active polymer, quantum dots, AIE active metal-organic framework and triphenylamine, not only in terms of their synthetic routes but also we outline their applications. Finally, we summarize our view of the construction and application of AIE-active molecules, which thus inspiring young researchers to explore new ideas, innovations, and develop the field of supramolecular chemistry in years to come.     

Restriction of Intramolecular Motions: The General Mechanism behind Aggregation‐Induced Emission

Aggregation‐induced emission (AIE) has been harnessed in many systems through the principle of restriction of intramolecular rotations (RIR) based on mechanistic understanding from archetypal AIE molecules such as tetraphenylethene (TPE). However, as the family of AIE‐active molecules grows, the RIR model cannot fully explain some AIE phenomena. Here, we report a broadening of the AIE mechanism through analysis of 10,10′,11,11′‐tetrahydro‐5,5′‐bidibenzo[a,d][7]annulenylidene (THBDBA), and 5,5′‐bidibenzo[a,d][7]annulenylidene (BDBA). Analyses of the computational QM/MM model reveal that the novel mechanism behind the AIE of THBDBA and BDBA is the restriction of intramolecular vibration (RIV). A more generalized mechanistic understanding of AIE results by combining RIR and RIV into the principle of restriction of intramolecular motions (RIM).     

Tetraphenylethylene-Based Hydrogen-Bonded Organic Frameworks (HOFs) with Brilliant Fluorescence

By synergistically employing four key strategies: (I) introducing tetraphenylethylene groups as the central core unit with aggregation-induced emission (AIE) properties, (II) optimizing the π-conjugated length by extending the building block branches, (III) incorporating flexible groups containing ethylenic bonds, and (IV) applying crystal engineering to attain dense stacking mode and highly twisty conformation, we successfully synthesized a series of hydrogen-bonded organic frameworks (HOFs) exhibiting exceptional one/two-photon excited fluorescence. Notably, when utilizing the fluorescently superior building block L2, HOF-LIFM-7 and HOF-LIFM-8 exhibiting high quantum yields (QY) of 82.1 % and 77.1 %, and ultrahigh two-photon absorption (TPA) cross-sections of 148959.5 GM and 123901.1 GM were achieved. These materials were successfully employed in one and two-photon excited lysosome-targeting cellular imaging. It is believed that this strategy, combining building block optimization and crystal engineering, holds significant potential for guiding the development of outstanding fluorescent HOF materials.     

Tetraphenylethylene and N-isopropylacrylamide block polymer-grafted carbon dots with their application in cellular imaging

Carbon dots (CDs) grafted with block polymer of tetraphenylethylene (TPE) and N-isopropylacrylamide (CD-g-poly(TPE-block-NIPAM)) were synthesized, which are aggregation-induced emission (AIE) nanoparticles. The CD-g-poly(TPE-block-NIPAM) exhibited different fluorescence behaviors in tetrahydrofuran (THF) and water. In THF, the CD-g-poly(TPE-block-NIPAM) could fluoresce, but only from CDs, and the TPE block showed no fluorescence. The fluorescence of CDs was quenched ,and the TPE block showed AIE, when the CD-g-poly(TPE-block-NIPAM) were dispersed in water. The CD-g-poly(TPE-block-NIPAM) showed no cytotoxicity, which could be easily internalized by human breast cancer cells and human embryonic kidney cells with high fluorescence, and they can be used as fluorescent tracers for living cells.     

Quantitative Prediction of Aggregation‐Induced Emission: A Full Quantum Mechanical Approach to the Optical Spectra

Full quantum mechanical (FQM) calculation of the excited state of aggregation‐induced‐emission (AIE) materials is highly sought but still a challenging task. Herein, we employed the recently developed electrostatically embedded generalized molecular fractionation (EE‐GMF) method, a method based on the systematic fragmentation approach, to predict, for the first time, the spectra of a prototype AIE fluorophore: di(p‐methoxylphenyl)dibenzofulvene (FTPE). Compared to the single molecular or QM/MM calculations, the EE‐GMF method shows significantly improved accuracy, nearly reproducing the experimental optical spectra of FTPE in both condensed phases. Importantly, we show that the conventional restriction of the intramolecular rotation mechanism cannot fully account for AIE, whereas the two‐body intermolecular quantum mechanical interaction plays a crucial role in AIE.     

Self-assembly of emissive metallocycles with tetraphenylethylene,BODIPY and terpyridine in one system

ABSTRACT

Tetraphenylethylene (TPE) related (supra)molecules have been intensively investigated due to their aggregation-induced emission (AIE) effect based on the restriction of intramolecular rotation (RIR). Meanwhile, boron-dipyrromethene (BODIPY) tends to emit intense fluorescence with high quantum yields. Herein, we combined TPE, BODIPY and terpyridine (TPY) into one system to study the emissive behaviour of organic building block as well as a self-assembled metallo-supramolecule. The TPY and BODIPY substituents with bulky sizes provide strong hindrance to restrict the rotation of the phenyl groups on TPE, leading to enhancement of emissive properties in both solution and aggregation states. Furthermore, the BODIPY-TPE-TPY ligand (L) was assembled with Zn (II) through coordination-driven self-assembly to form a cyclic dimer (D) with typical AIE characteristics.     

AIE-based nanoaggregate tracker: high-fidelity visualization of lysosomal movement and drug-escaping processes

High-fidelity imaging and long-term visualization of lysosomes are crucial for their functional evaluation, related disease detection and active drug screening. However, commercial aggregation-caused quenching probes are not conducive to precise lysosomal imaging because of their inherent drawbacks, like easy diffusion, short emission and small Stokes shift, let alone their long-term tracing due to rapid photobleaching. Herein we report a novel aggregation-induced emission (AIE)-based TCM-PI nanoaggregate tracker for direct visualization of lysosomes based on the building block of tricyano-methylene-pyridine (TCM), wherein introduced piperazine (PI) groups behave as targeting units to lysosomes upon protonation, and the self-assembled nanostructure contributes to fast endocytosis for enhanced targeting ability as well as extended retention time for long-term imaging. The piperazine-stabilized TCM-PI nanoaggregate shifts the emission maximum to 677 nm in an aqueous environment, and falls within the desirable NIR region with a large Stokes shift of 162 nm, thereby greatly reducing biological fluorescent background interference. In contrast with the commercially available LysoTracker Red, the essential AIE characteristic of high photostability can guarantee three-dimensional high-fidelity tracing with low photobleaching, and little diffusion from lysosomes, and especially overcome the AIE bottleneck to target specificity. Consequently, the AIE-based nanoaggregate tracker successfully achieves the high-fidelity and long-term tracing of lysosomal movement and even monitors the drug-escaping process from lysosomes to cell nuclei, which provides a potential tool to benefit drug screening.

Well-formed AIE nanoaggregates with good stability can achieve high-fidelity visualization of lysosomal movement and drug-escaping processes.     

Aggregation-induced multicolor luminescent nanoparticles with adaptive and fixed cores derived from brominated tetraphenylethene-containing block copolymer

Aggregation-induced emission (AIE)-active nanoparticles (NPs) exhibiting multicolor fluorescence and high-quantum yields independent of the environment are important for the further development of next-generation smart fluorescent materials. In this work, AIE-active amphiphilic block copolymers were designed and synthesized by RAFT polymerization of a brominated tetraphenylethene (TPE)-containing acrylate (A-TPE-Br). The block copolymer exhibited typical AIE effects in selective solvents, which can be explained by hydrophobic TPE aggregated in the core during micelle formation. Luminescent core–shell NPs with a crosslinked AIE core (fixed structure) were synthesized by the Suzuki coupling reaction of the bromine groups of the assembled block copolymer and boronic acid compounds. The NPs composed of TPE/thiophene crosslinked core showed green emission in both diluted state and solid state, implying the ability to fluoresce regardless of environmental changes and molecular dispersion. Multicolor luminescent NPs capable of changing color from blue to red were synthesized by changing the coupling compounds, such as anthracene for electron-rich units and benzothiadiazole for electron-deficient units. The effects of the nature of the donor and acceptor, as well as their combination (TPE/donor/acceptor sequence), on the color and fluorescent intensity of the core crosslinked NPs in the nonpolar and polar solvents, and solid state, were investigated.     

Luminescent core–shell nanoparticles with crosslinked aggregation-induced emission core structures: Emission both in solution and solid states

Luminescent core–shell nanoparticles (NPs) with crosslinked aggregation-induced emission (AIE) core structures, which exhibited excellent emission independent of the dispersion state of the NPs, have been developed by a facile one-pot method based on the self-assembly of an amphiphilic block copolymer poly(PEGMA)-b-poly(DB3VT). Core–shell micelles with a poly(DB3VT) core were formed from poly(PEGMA)-b-poly(DB3VT) in tetrahydrofuran (THF)/H₂O condition, and the crosslinked AIE-based structure was selectively incorporated into the core by the Suzuki coupling reaction between poly(DB3VT) blocks and tetraphenylethylene (TPE)-based coupling monomers at the same time. This method afforded a uniform NP with a crosslinked TPE-based AIE core structure. The obtained NP exhibited excellent emission both in diluted solution and solid states. This result indicated that the formed TPE-based AIE core structure was always aggregated regardless of NP dispersion owing to the crosslinking as we expected. The crosslinked TPE-based AIE core structure, which was related to the emission property, was readily tuned by the selection and combination of coupling monomers in the Suzuki coupling reaction. By incorporating electron-deficient units into the core, the emission color could be successfully tuned from yellow-green to orange and red while maintaining the emission property independent of the state of the NP dispersion. These results demonstrated that NPs with the crosslinked AIE core structures are a promising luminescent material design motif to realize emission independent on molecular dispersion.     

Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission

Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission (AIE) were prepared from amphiphilic block copolymers PEG-b-PTPEMA where the hydrophobic block PTPEMA was a polymethacrylate with tetraphenylethene (TPE) as the AIE side group. Four highly asymmetric block copolymers with hydrophilic block weight ratio f_PEG ≤ 20% were synthesized. Cubosomes and hexosomes with strong fluorescence emission were obtained by nanoprecipitation of polymers with f_PEG < 9% in dioxane/water and THF/water systems. Their ordered internal structures were studied by electron microscopy (cryo-EM, SEM and TEM) and the X-ray scattering technique (SAXS). To elucidate the formation mechanisms of these inverted colloids, other parameters influencing the morphologies, like the water content during self-assembly and the organic solvent composition, were also investigated. This study not only inspires people to design novel building blocks for the preparation of functional cubosomes and hexosomes, but also presents the first AIE fluorescent polymer cubosome and hexosome with potential applications in bio-related fields.

Fluorescent Im$\bar{3}$m cubosome and P6mm hexosome with aggregation-induced emission (AIE) were reported, which were formed by amphiphilic block copolymers PEG-b-PTPEMA. The length of hydrophobic block PTPEMA was adjusted to control morphology formation.     

Highlights on the Road towards Highly Emitting Solid‐State Luminophores: Two Classes of Thiazole‐Based Organoboron Fluorophores with the AIEE/AIE Effect

Developing a novel, small‐sized molecular building block that may be capable of emitting light in the solid state is a challenging task and has rarely been reported in the literature. BF₂‐containing dyes seem to be promising candidates towards this aim. Two series of new N^NBF₂ complexes showing aggregation‐induced emission (AIE) and aggregation‐induced emission enhancement (AIEE) were designed and synthesized by means of a new protocol, which improved on the traditional method by employing microwave irradiation. The optical and photophysical properties of the BF₂ complexes were investigated in depth. The synthesized complexes showed fluorescence in both solution and the solid state and, in a mixture of tetrahydrofuran/water, may aggregate into fluorescent nanoparticles. The experimental investigation was supported by quantum mechanical calculations. Their availability, stability, large Stokes shifts, and aggregation capabilities, along with their solid‐state emission capability, render this new class of BF₂ complexes promising AIEE/AIE fluorophores for further applications in the fields of fluorescence imaging and materials science.     

末端四苯乙烯荧光团标记法研究双亲性嵌段聚合物的自组装行为

以四苯乙烯类分子2-溴-2-甲基-丙酸-3-(4-三苯乙烯基-苯氧基)-丙醇酯(E)作为引发剂,N-异丙基丙烯酰胺和苯乙烯为原料,通过活性自由基聚合,合成了末端具有聚集诱导发光(AIE)活性发光体的双亲性嵌段聚合物G。 详细研究了AIE活性引发剂E和嵌段聚合物G在不同状态下的光物理行为差异。结果表明,在相同浓度条件下,随着温度的升高,引发剂E分散液的荧光强度不断下降。 而嵌段聚合物的荧光强度先上升,当温度超过37 ℃后,嵌段聚合物的荧光强度不断下降。 同样地,通过改变引发剂E和嵌段聚合物G在四氢呋喃和水混合溶剂中的浓度发现,随着浓度的减小,引发剂E的荧光强度不断下降,而嵌段聚合物分散液在改变分散液浓度时荧光强度的变化规律和改变温度时荧光强度的变化趋势相似。 通过监控双亲性嵌段聚合物末端挂接的AIE活性发光分子发光性质的变化可以间接表征其聚集态结构的变化。     

可双光子激发的聚集诱导发光光敏剂及其生物医学应用

综合评述了双光子激发的聚集诱导发光(AIE)光敏剂的研究进展, 重点讨论了双光子激发的AIE光敏剂的设计思路及在生物医学中的应用, 并对其发展前景进行了展望.     

Aggregation-induced emission of siloles

Aggregation-induced emission (AIE) is a unique and significant photophysical phenomenon that differs greatly from the commonly acknowledged aggregation-caused emission quenching observed for many π-conjugated planar chromophores. The mechanistic decipherment of the AIE phenomenon is of high importance for the advance of new AIE systems and exploitation of their potential applications. Propeller-like 2,3,4,5-tetraphenylsiloles are archetypal AIE-active luminogens, and have been adopted as a core part in the design of numerous luminescent materials with diverse functionalities. In this review article, we elucidate the impacts of substituents on the AIE activity and shed light on the structure–property relationship of siloles, with the aim of promoting the judicious design of AIE-active functional materials in the future. Recent representative advances of new silole-based functional materials and their potential applications are reviewed as well.     

Zinc (II) and AIEgens: The “Clip Approach” for a Novel Fluorophore Family. A Review

Aggregation-induced emission (AIE) compounds display a photophysical phenomenon in which the aggregate state exhibits stronger emission than the isolated units. The common term of “AIEgens” was coined to describe compounds undergoing the AIE effect. Due to the recent interest in AIEgens, the search for novel hybrid organic–inorganic compounds with unique luminescence properties in the aggregate phase is a relevant goal. In this perspective, the abundant, inexpensive, and nontoxic d¹⁰ zinc cation offers unique opportunities for building AIE active fluorophores, sensing probes, and bioimaging tools. Considering the novelty of the topic, relevant examples collected in the last 5 years (2016–2021) through scientific production can be considered fully representative of the state-of-the-art. Starting from the simple phenomenological approach and considering different typological and chemical units and structures, we focused on zinc-based AIEgens offering synthetic novelty, research completeness, and relevant applications. A special section was devoted to Zn(II)-based AIEgens for living cell imaging as the novel technological frontier in biology and medicine.     

Study of aggregation induced emission of cyano-substituted oligo (p-phenylenevinylene) by femtosecond time resolved fluorescence

The aggregation induced emission (AIE) mechanism of the cyano-substituted oligo (p-phenylenevinylene)1,4-bis [1-cyano-2-(4-(diphenylamino) phenyl) vinyl] benzene (TPCNDSB) is investigated by time resolved fluorescence technique. By reconstructing the time resolved emission spectra (TRES), it is found that in solvent of low polarity, the emission is mainly from the local emission (LE) state with high quantum yield, but in high polarity solvent, the emission is mainly from the intramolecular charge transfer (ICT) state, which is a relatively dark state, with low quantum yield. In crystal form, the restriction of transfer from LE state to ICT state results in efficient AIE.     

具有聚集诱导发光特性的四苯基乙烯研究进展

具有聚集诱导发光(aggregation-induced emission,AIE)性质的四苯基乙烯及其衍生物(tetraphenylethenes,TPEs)因其发光性能优良、合成简便、易多功能化而越来越受到关注.本文着重对最近几年TPEs的AIE性质研究进展进行综述.在阐述结构与AIE性质之间关系的同时,介绍了TPEs在生物、化学传感器及其它方面的应用, 并对TPEs的设计与应用给予展望.     

Aggregation-induced Emission Materials for High-efficiency Perovskite Solar Cells

The perovskite solar cells (PSCs) with high efficiency and stability are in great demand for commercial applications. Although the remarkable photovoltaic feature of perovskite layer plays a great role in improving the PCE of PSCs, the inevitable defects and poor stability of perovskite, etc. are the bottleneck and restrict the commercialization of PSCs. Herein, a review provides a strategy of applying aggregation-induced emission (AIE) molecules, containing passivation functional groups and distinct AIE character, which serves as the alternative materials for fabricating high-efficiency and high-stability PSCs. The methods of introducing AIE molecules to PSCs are also summarized, including additive engineering, interfacial engineering, hole transport materials and so on. In addition, the functions of AIE molecule are discussed, such as defects passivation, morphology modulation, well-matched energy level, enhanced stability, hole transport ability, carrier recombination suppression. Finally, the detailed functions of AIE molecules are offered and further research trend for high performance PSCs based on AIE materials is proposed.