Bridged Stilbenes: AIEgens Designed via a Simple Strategy to Control the Non‐radiative Decay Pathway

To broaden the application of aggregation‐induced emission (AIE) luminogens (AIEgens), the design of novel small‐molecular dyes that exhibit high fluorescence quantum yield (Φ_fl) in the solid state is required. Considering that the mechanism of AIE can be rationalized based on steric avoidance of non‐radiative decay pathways, a series of bridged stilbenes was designed, and their non‐radiative decay pathways were investigated theoretically. Bridged stilbenes with short alkyl chains exhibited a strong fluorescence emission in solution and in the solid state, while bridged stilbenes with long alkyl chains exhibited AIE. Based on this theoretical prediction, we developed the bridged stilbenes BPST[7] and DPB[7], which demonstrate excellent AIE behavior.     

Investigating the effects of side chain length on the AIE properties of water-soluble TPE derivatives

The emissive properties of fluorophores in aggregated state are important for the development of bio-sensors or bio-imaging reagents. So three water-soluble TPE derivatives with different lengths of side chains have been synthesized and we investigated the effects of side chains on aggregation-induced emission (AIE) properties in the aggregated states. The results indicate that side chains on the fluorophores play a pivotal role in their emission in aggregated state mediated by heparin or solid state, because the coplanarity of these TPE derivatives was affected by side chains. The rates of radiative decay k_f and non-radiative decay k_nr have been obtained through the quantum yields and lifetime, and a larger k_f and smaller k_nr were present for compound TPE-C4N, suggesting that the aggregated TPE-C4N should posses the most remarkable fluorescent property.     

Photoinduced dynamics of a cyanine dye: parallel pathways of non-radiative deactivation involving multiple excited-state twisted transients

Cyanine dyes are broadly used for fluorescence imaging and other photonic applications. 3,3′-Diethylthiacyanine (THIA) is a cyanine dye composed of two identical aromatic heterocyclic moieties linked with a single methine, –CH. The torsional degrees of freedom around the methine bonds provide routes for non-radiative decay, responsible for the inherently low fluorescence quantum yields. Using transient absorption spectroscopy, we determined that upon photoexcitation, the excited state relaxes along two parallel pathways producing three excited-state transients that undergo internal conversion to the ground state. The media viscosity impedes the molecular modes of ring rotation and preferentially affects one of the pathways of non-radiative decay, exerting a dominant effect on the emission properties of THIA. Concurrently, the polarity affects the energy of the transients involved in the decay pathways and further modulates the kinetics of non-radiative deactivation.     

Aggregation‐Induced Emission (AIE): A Historical Perspective

Aggregation‐induced emission (AIE) has attracted considerable interest over the last twenty years. In contrast to the large number of available reviews focusing specifically on AIE, this Essay discusses the AIE phenomenon from a broader perspective, with an emphasis on early observations related to AIE made long before the term was coined. Illustrative examples are highlighted from the 20th century where fluorescence enhancement upon rigidification of dyes in viscous or solid environments or J‐aggregate formation was studied. It is shown that these examples already include typical AIE luminogens such as tetraphenylethylene (TPE) as well as stilbenes and oligo‐ or polyphenylenevinylenes and ‐ethynylenes, which became important fluorescent solid‐state materials in OLED research in the 1990s. Further examples include cyanine dyes such as thiazole orange (TO) or its dimers (TOTOs), which have been widely applied as molecular probes in nucleic acid research. The up to 10 000‐fold fluorescence enhancement of such dyes upon intercalation into double‐stranded DNA, attributable to the restricted intramolecular motion (RIM) concept, afforded commercial products for bioimaging and fluorescence sensing applications already in the early 1990s.     

Ring Size Effects on Multi‐Stimuli Responsive Luminescent Properties of Cyclic Amine Substituted β‐Diketones and Difluoroboron Complexes

Emissive β‐diketones (bdks) and difluoroboron complexes (BF₂bdks) show multi‐stimuli responsive luminescence in both solution and the solid state. A series of bdk ligands and boron coordinated dyes were synthesized with different cyclic amine substituents in the 4‐position to explore ring size effects on various luminescent properties, including solvatochromism, viscochromism, aggregation‐induced emission (AIE), mechanochromic luminescence (ML) and halochromism. Red‐shifted absorption and emission were observed in CH₂Cl₂ for both bdk ligands and boron dyes with increasing substituent ring size. The compounds displayed bathochromic emission in more polar solvents, and higher fluorescence intensity in more viscous media. The AIE compounds exhibited enhanced emission when aggregated. For solid‐state properties, a large emission wavelength shift was shown for the piperidine substituted bdk after melt quenching on weighing paper. Large blue‐shifted emissions were observed in all the boron dye spin cast films after trifluoroacetic acid vapor annealing, and the original emissions were partially recovered after triethylamine vapor treatment.     

Enhanced emission efficiency and excited state lifetime due to restricted intramolecular motion in silole aggregates

The aggregation-induced emission (AIE) properties of 1,1,2,3,4,5-hexaphenylsilole (HPS) and poly{11-[(1,2,3,4,5-pentaphenylsilolyl)oxy]-1-phenyl-1-undecyne} (PS9PA) were studied by time-resolved fluorescence technique. The enhanced fluorescence and long fluorescent lifetime were obtained for the sample in an aggregate state as compared to the sample in solution. The time-decay of fluorescence of HPS and PS9PA in high viscosity solvents and low-temperature glasses has also been measured in detail to further investigate the possible mechanism for AIE. Enhanced light emission and long fluorescence lifetime were detected for both HPS and PS9PA in the solution-thickening and -cooling experiments. These results provided direct evidence that the enhanced photoluminescence (PL) efficiency is due to restricted intramolecular motion, which ascribes AIE to the deactivation of nonradiative decay caused by restricted torsional motions of the molecules in the solid state or aggregate form.     

Alkynylgold(I) C3-Chiral Concave Complexes: Aggregation and Luminescence

Chiral gold(I) acetylide trinuclear complexes 1 – 3 based on the cyclotribenzylene platform and terminal PR₃ ligands (R=Ph, Et, and Cy, respectively), were characterized and their light emission studied. They exhibited long-lived blue phosphorescence in CHCl₃ and a weak fluorescence in the UV. In MeOH/CHCl₃ mixtures of >1:1 volume ratio, 1 and 2 exhibited a new emission band at ca. 540 nm that developed at the expense of the UV emission. DLS studies demonstrated the presence of molecular aggregates of Ø 30–80 nm. The green emission observed in MeOH-rich solvent mixtures was therefore induced by aggregation, and could originate from Au⋅⋅⋅Au interactions. The AIE spectrum of 3 was observed only in solutions containing 99 % of MeOH, and correlated with its solid state emission. The AIE profiles of the enantiomers of 1 differed from that of rac- 1 , suggesting that the latter is a true racemate.     

Tuning Emission Wavelength of Polymorphous Crystal via Controllable Alkyl Chain Stacking and Its Vapor- and Thermo-Responsive Fluorescence

Tuning fluorescence colour of solid-state materials has become a topic of increasing interest for both fundamental mechanism study and practical applications such as sensors, optical recording and security printing. In this work, a fluorescent colour tuneable molecule BA-C16 is rationally designed and facilely synthesized by attaching flexible long alkyl chains to 2-hydroxybenzophenone azine ( BA ), which shows both aggregation-induced emission (AIE) and excited-state intramolecular proton transfer (ESIPT) characteristics. Compared to BA , the simple introduction of long alkyl chains in BA-C16 leads to an emission wavelength redshift from 542 to 558 nm. This strategy of extending emission wavelength is rarely reported, and is ascribed to the enlarged through-space π-conjugation between interplanar molecules in the aggregate of BA-C16 . Three crystals of BA-C16 are obtained with green, yellowish green and yellow emission. According to characterization by X-ray crystallography, X-ray powder diffraction and differential scanning calorimetry, alkyl chains play an important role in inducing different stacking modes of the three crystals, which further leads to polymorph-dependent fluorescence colour. BA-C16 exhibits tuneable solid-state fluorescence upon vapor fumigation, or annealing based on a transition between a “near-monomer” crystalline state and a “dimer” crystalline state. BA-C16 is further applied for rewritable fluorescence printing tuned by vapor- and thermal-treatment.     

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.     

A Facilely Synthesized Dual-State Emission Platform for Picric Acid Detection and Latent Fingerprint Visualization

To achieve a highly efficient, dual-state emission platform for picric acid (PA) detection and latent fingerprint (LFP) visualization, flexible alkyl chains have been facilely attached to the commercial organic dye 3,4,9,10-perylenetetracarboxylic dianhydride to provide the target perylenetetracarboxylate molecules PTCA-C4, PTCA-C6, and PTCA-C12. Interestingly, all these molecules exhibited impressive fluorescence characteristics with high photoluminescence quantum yields (PLQYs) of around 93.0 % in dilute solution. Also, emissive features were observed in the solid state because close molecular packing is prevented by the alkyl chains, especially for PTCA-C6, which has a high PLQY value of 49.0 %. Benefiting from its impressive fluorescence performance in both solution and as aggregates, PTCA-C6 was used as a dual-state emission platform for PA detection and also LFP visualization. For example, double-responsive fluorescence quenching in solution was observed in PA detection studies, resulting in high quenching constants (K_SV) and also low limit-of-detection values. Furthermore, the fingerprint powder based on PTCA-C6 also presented an impressive performance on various substrates in terms of fluorescence intensity and resolution, clearly providing the specific fine details of latent fingerprints. These results demonstrate that the facilely synthesized PTCA-C6 with efficient dual-state emission exhibits great potential in the real-world applications of PA detection and LFP visualization.     

AIE Ligand Constructed Zn(Ⅱ)Complex with Reversible Photo-induced Color and Emission Changes

Fluoran salicylaldehyde hydrazone metal complex(FSHMC)is a kind of recently reported photo-responsive system,which has the advantages of simple synthesis,multiple colors as well as distinct color change before and after UV light irradiation.However,the emission property of FSHMC is relatively unitary.In solid state,especially,only fluorescence quench is induced after UV light irradiation,which limits their applications.In this work,a typical aggregation-induced emission(AIE)moiety of tetraphenylethene(TPE)was introduced to the design of FSHMC.The obtained FSHMC,2-Zn,exhibited reversible color and fluorescence changes upon UV light irradiation.Due to the AIE feature of compound 2,2-Zn exhibited different emission changes upon UV light irradiation in THF and in solid matrix,because of the fluorescence resonance energy transfer(FRET)process from TPE moiety to rhodamine B moiety.     

Unusual Aggregation‐Induced Emission of a Coumarin Derivative as a Result of the Restriction of an Intramolecular Twisting Motion

Aggregation‐induced emission (AIE) is commonly observed for propeller‐like luminogens with aromatic rotors and stators. Herein, we report that a coumarin derivative containing a seven‐membered aliphatic ring (CD‐7) but no rotors showed typical AIE characteristics, whereas its analogue with a five‐membered aliphatic ring (CD‐5) exhibited an opposite aggregation‐caused quenching (ACQ) effect. Experimental and theoretical results revealed that a large aliphatic ring in CD‐7 weakens structural rigidity and promotes out‐of‐plane twisting of the molecular backbone to drastically accelerate nonradiative excited‐state decay, thus resulting in poor emission in solution. The restriction of twisting motion in aggregates blocks the nonradiative decay channels and enables CD‐7 to fluoresce strongly. The results also show that AIE is a general phenomenon and not peculiar to propeller‐like molecules. The AIE and ACQ effects can be switched readily by the modulation of molecular rigidity.     

An Organic Molecule with Asymmetric Structure Exhibiting Aggregation‐Induced Emission,Delayed Fluorescence,and Mechanoluminescence

Compounds displaying delayed fluorescence (DF), from severe concentration quenching, have limited applications as nondoped organic light‐emitting diodes and material sciences. As a nondoped fluorescent emitter, aggregation‐induced emission (AIE) materials show high emission efficiency in their aggregated states. Reported herein is an AIE‐active, DF compound in which the molecular interaction is modulated, thereby promoting triplet harvesting in the solid state with a high photoluminescence quantum yield of 93.3 %, which is the highest quantum yield, to the best of our knowledge, for long‐lifetime emitters. Simultaneously, the compound with asymmetric molecular structure exhibited strong mechanoluminescence (ML) without pretreatment in the solid state, thus exploiting a design and synthetic strategy to integrate the features of DF, AIE, and ML into one compound.     

An Organic Molecule with Asymmetric Structure Exhibiting Aggregation‐Induced Emission,Delayed Fluorescence,and Mechanoluminescence

Compounds displaying delayed fluorescence (DF), from severe concentration quenching, have limited applications as nondoped organic light‐emitting diodes and material sciences. As a nondoped fluorescent emitter, aggregation‐induced emission (AIE) materials show high emission efficiency in their aggregated states. Reported herein is an AIE‐active, DF compound in which the molecular interaction is modulated, thereby promoting triplet harvesting in the solid state with a high photoluminescence quantum yield of 93.3 %, which is the highest quantum yield, to the best of our knowledge, for long‐lifetime emitters. Simultaneously, the compound with asymmetric molecular structure exhibited strong mechanoluminescence (ML) without pretreatment in the solid state, thus exploiting a design and synthetic strategy to integrate the features of DF, AIE, and ML into one compound.     

A new 2D cadmium chloride network with 2-aminopyrimidine displaying long lifetime photoluminescence emission

The hydrothermal reaction of CdCl₂ with 2-aminopyrimidine in water yields a 2D metal-organic coordination framework [CdCl₂(PymNH₂)] (1) (PymNH₂ = 2-aminopyrimidine). This compound consists of Cd₂(μ-Cl)₂ corner-sharing chains bridged by PymNH₂ through the endocyclic ring nitrogen atoms. Interestingly, this polymer exhibits long lifetime photoluminescence emission at room temperature in the solid state with long lifetimes decay.     

Structural and process controls of AIEgens for NIR-II theranostics

Aggregation-induced emission (AIE) is a cutting-edge fluorescence technology, giving highly-efficient solid-state photoluminescence. Particularly, AIE luminogens (AIEgens) with emission in the range of second near-infrared window (NIR-II, 1000–1700 nm) have displayed salient advantages for biomedical imaging and therapy. However, the molecular design strategy and underlying mechanism for regulating the balance between fluorescence (radiative pathway) and photothermal effect (non-radiative pathway) in these narrow bandgap materials remain obscure. In this review, we outline the latest achievements in the molecular guidelines and photophysical process control for developing highly efficient NIR-II emitters or photothermal agents with aggregation-induced emission (AIE) attributes. We provide insights to optimize fluorescence efficiency by regulating multi-hierarchical structures from single molecules (flexibilization) to molecular aggregates (rigidification). We also discuss the crucial role of intramolecular motions in molecular aggregates for balancing the functions of fluorescence imaging and photothermal therapy. The superiority of the NIR-II region is demonstrated by fluorescence/photoacoustic imaging of blood vessels and the brain as well as photothermal ablation of the tumor. Finally, a summary of the challenges and perspectives of NIR-II AIEgens for in vivo theranostics is given.

Structural and process controls of NIR-II AIEgens realize manipulating of radiative (R) and nonradiative (NR) decay for precise theranostics.     

Benzo[b]phosphole‐Containing π‐Electron Systems: Synthesis Based on an Intramolecular trans‐Halophosphanylation and Some Insights into Their Properties

The intramolecular trans‐halophosphanylation of 2‐(aminophosphanyl)phenylacetylenes mediated by PBr₃ followed by the oxidation with H₂O₂, produces 3‐bromobenzo[b]phosphole oxide derivatives. This cyclization is also used for the synthesis of a 3‐iodo derivative by conducting the reaction in the presence of LiI. Based on this synthetic method, various benzophosphole‐containing π‐conjugated compounds, including a phosphoryl and methylene‐bridged stilbene 10 , 2,3,6,7‐tetraphenylbenzo[1,2‐b:4,5‐b′]diphosphole‐P,P′‐dioxides 11 , and their phosphine sulfide derivatives 12 , are synthesized. The study of the structure–property relationships in a series of the bridged stilbenes, including a bis(methylene)‐bridged stilbene 10 , and a bis(phosphoryl)‐bridged stilbene, reveals that as the contribution of the phosphoryl groups increased, the absorption and emission maxima substantially shift to longer wavelengths. The intrinsic substituent effects of the phosphoryl group in this skeleton are to decrease the oscillator strength of the electronic transition and thus decrease the radiative decay rate constants from the singlet excited state. Nevertheless, these compounds maintain high fluorescence quantum yields (Φ_F>0.8) owing to the significantly retarded nonradiative decay process. In the study of the benzodiphosphole derivatives 11 and 12 , their cyclic voltammetry revealed that both of the phosphoryl and phosphine sulfide derivatives have low reduction potentials (?1.7 to ?1.8 V vs ferrocene/ferrocenium couple) with the high reversibility of the redox waves. These compounds also showed high thermal stabilities with the high glass transition temperatures of 147–159 °C, indicative of their potential utilities as amorphous materials.     

Principles of Aggregation-Induced Emission: Design of Deactivation Pathways for Advanced AIEgens and Applications

Twenty years ago, the concept of aggregation-induced emission (AIE) was proposed, and this unique luminescent property has attracted scientific interest ever since. However, AIE denominates only the phenomenon, while the details of its underlying guiding principles remain to be elucidated. This minireview discusses the basic principles of AIE based on our previous mechanistic study of the photophysical behavior of 9,10-bis(N,N-dialkylamino)anthracene ( BDAA ) and the corresponding mechanistic analysis by quantum chemical calculations. BDAA comprises an anthracene core and small electron donors, which allows the quantum chemical aspects of AIE to be discussed. The key factor for AIE is the control over the non-radiative decay (deactivation) pathway, which can be visualized by considering the conical intersection (CI) on a potential energy surface. Controlling the conical intersection (CI) on the potential energy surface enables the separate formation of fluorescent (CI:high) and non-fluorescent (CI:low) molecules [control of conical intersection accessibility ( CCIA )]. The novelty and originality of AIE in the field of photochemistry lies in the creation of functionality by design and in the active control over deactivation pathways. Moreover, we provide a new design strategy for AIE luminogens (AIEgens) and discuss selected examples.     

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.