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Aggregation-Induced Electrochemiluminescence of Carboranyl Carbazoles in Aqueous Media
摘要： The aggregation-induced electrochemiluminescence (AIECL) of carboranyl carbazoles in aqueous media was investigated for the first time. Quantum yields, morphologies, and particle sizes were observed to determine the electrochemiluminescence (ECL) performance of these aggregated organic dots (ODs). All compounds exhibit much higher ECL stability and intensity than the carborane-free compound, demonstrating the essential role of the carboranyl motif. Moreover, the results of cyclic voltammetry (CV) suggest that redox take place at the carboranyl motif. The excited states of ODs were proposed to be generated by the mechanism of surface state transitions. More importantly, these compounds with reductive-oxidative mechanism is exclusive from other organic materials with oxidative-reductive mechanism. Our experiments and data have established the relation between AIE organic structures and ECL properties that has a strong potential for biological and diagnostic applications.
关键词： aggregation induced emission,boron cluster,organic dots,carborane,electrochemiluminescence
更新于2025-09-19 17:15:36
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Aggregation-induced emission (AIE)-active molecules bearing singlet oxygen generation activities: the tunable singlet–triplet energy gap matters
摘要： Herein, a series of photosensitizers were constructed of a, b and c-isomers of terpyridine and the corresponding N-methylation derivatives. Benefiting from the tunable singlet–triplet energy gap and aggregation-induced emission characteristics, two-photon active photosensitizers L2b and L2c showed relatively strong intersystem crossing facilitating 1O2 generation and cell apoptosis with near-infrared excitation.
关键词： Aggregation-induced emission,singlet oxygen generation,photodynamic therapy,photosensitizers,two-photon excitation
更新于2025-09-19 17:15:36
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Ultrafast fabrication of fluorescent organic nanoparticles with aggregation-induced emission feature through the microwave-assisted Biginelli reaction
摘要： Because of its unique optical properties, the aggregation-induced emission (AIE) dye has attracted extensive attention for various applications. Especially, the utilization of AIE-active dyes for fabrication of fluorescent organic nanoparticles (FONs) has attracted the most research interest for biomedical applications. Therefore, the development of novel and effective strategies to design and prepare AIE-active FONs should be of great importance for the biomedical applications of AIE-active FONs. In this report, we reported an ultrafast strategy that based on the one-pot microwave-assisted Biginelli reaction for fabrication of AIE-active poly(AA-AEMA-TPE) copolymers, which use the 2-(methacryloyoxy) ethylacet, acrylic acid (AA) and 4',4'''-(1,2-diphenylethene-1,2-diyl) bis([1,1'-biphenyl]-4-carbaldehyde) (TPE-CHO) as the substrates. The microwave-assisted Biginelli reaction is simple, efficient and atom-economical and can be accomplished within 3 min. Owing to their amphiphilicity, poly(AA-AEMA-TPE) copolymers will self-assemble into FONs with small size and high water dispersibility. The proton nuclear magnetic resonance (1H NMR) spectroscopy, UV-Vis spectrum and fluorescence spectrometer were used to characterize the resultant copolymers. We demonstrated that poly(AA-AEMA-TPE) FONs possess many excellent properties, such as high water dispersibility, intense fluorescence, obvious AIE feature and favorable biocompatibility. The above results suggest that poly(AA-AEMA-TPE) FONs are of great potential for fluorescent imaging. Moreover, the microwave-assisted Biginelli reaction can occur under a rather benign environment with high efficiency and good substrate adaptability. Therefore, we believe that the method developed in this work could greatly advance the applications of AIE-active functional materials.
关键词： microwave-assisted Biginelli reaction,biological imaging,fluorescent polymer nanoparticles,Aggregation-induced emission,living controlled polymerization
更新于2025-09-19 17:15:36
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Luminescent Cyclic Trinuclear Coinage Metal Complexes with Aggregation-Induced Emission (AIE) Performance
摘要： A series of AIE active cyclic trinuclear complexes (Au3, Ag3, and Cu3) have been successfully prepared and elucidated by X-ray crystallography. These complexes showed excellent AIE properties and their quantum yields (QYs) were significantly increased compared to that of the free ligands. The remarkable solution induced AIE activity in atom-precise coinage metal complexes is still scarce, and this work opens a promising avenue for the development of easily prepared metal-based AIE luminogens with high emission efficiency.
关键词： Aggregation-Induced Emission,X-ray Crystallography,Quantum Yields,Coinage Metal Complexes,Luminescence
更新于2025-09-19 17:15:36
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Imidazole-containing cyanostilbene-based molecules with aggregation-induced emission characteristics: photophysical and electroluminescent properties
摘要： Organic luminogens with aggregation-induced emission (AIE) characteristics have recently attracted great research interest due to their excellent luminescence behavior in the aggregate state. Cyanostilbene is a well-known AIE-active moiety due to its unique luminescence mechanism and widespread use in the design of optical materials. In this work, we report two symmetrical imidazole-containing cyanostilbene derivatives with AIE activity, abbreviated as TPIA and PPIA, whose chemical structures only differ by a C–C bond. Both molecules are thermally stable and fabricated as electroluminescent (EL) devices. On one hand, the study of their photophysical properties confirms that the restricted intramolecular rotation (RIR) effect is still the dominant factor for the AIE effect in these two cyanostilbene-based molecules. On the other hand, the EL results reveal that a more conjugated molecular structure is beneficial for the EL properties. Moreover, the optimization of the device configuration with an electron-blocking layer significantly improves the EL performance. The orange-emissive PPIA-based device shows a high external quantum efficiency of 1.02% with a small efficiency roll-off.
关键词： Imidazole,Aggregation-induced emission,Cyanostilbene,OLEDs,Electroluminescence
更新于2025-09-19 17:15:36
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Rhodamine-naphthalimide demonstrated a distinct aggregation-induced emission mechanism: elimination of dark-states <i>via</i> dimer interactions (EDDI)
摘要： Rhodamine B-naphthalimide (RhB-Naph) demonstrated a distinct aggregation-induced emission (AIE) mechanism, different from the restriction of intramolecular rotations or vibrations as in traditional AIE molecules. The monomers of RhB-Naph were non-emissive, due to the presence of a dark S1 state. Upon molecular aggregation, intermolecular interactions significantly altered the electronic properties of RhB-Naph, leading to the formation of a bright S1 state and endowing RhB-Naph with notable AIE properties. Besides, we demonstrated that RhB-Naph enabled the development of a solid-state three-color fluorescent switch upon multi-external stimuli.
关键词： fluorescent switch,dark state,dimer interactions,rhodamine-naphthalimide,aggregation-induced emission
更新于2025-09-19 17:15:36
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Achievement of Higha??Performance Nondoped Blue OLEDs Based on AIEgens via Construction of Effective Higha??Lying Chargea??Transfer State
摘要： There remains an urgent demand for high-quality blue luminogens that can simultaneously achieve high photoluminescence quantum yield (PLQY) in film and high exciton utilization efficiency (EUE) in the electroluminescence (EL) process. In this study, a referable molecular design strategy is developed for blue luminogens via constructing low-lying locally excited (LE) state with an aggregation-induced emission (AIE) characteristic and high-lying charge-transfer (CT) state for the effective triplet-to-singlet conversion channel. 2TriPE-BPI-MCN with the insertion of p-cyano and o-methyl groups is designed to compare with its matrix framework (2TriPE-BPI). They have analogous properties of the lowest singlet (S1) states with blue emission and free of concentration quenching in film; however, 2TriPE-BPI-MCN exhibits unusual response for hydrostatic pressure owing to its S2 state CT characteristics. Therefore, 2TriPE-BPI-MCN can harness more electrogenerated excitons than 2TriPE-BPI, resulting in a better EL performance in nondoped blue organic light-emitting diodes (OLEDs) (CIEx,y = 0.153, 0.147) with high external quantum efficiency of 4.6% and negligible efficiency roll-off. These findings could open a feasible avenue to develop high-quality blue luminogens for high-performance nondoped blue OLEDs.
关键词： organic light-emitting diodes,blue emission,hydrostatic pressure,aggregation-induced emission,charge-transfer state
更新于2025-09-19 17:13:59
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Bioinspired Simultaneous Changes in Fluorescence Color, Brightness, and Shape of Hydrogels Enabled by AIEgens
摘要： Development of stimuli-responsive materials with complex practical functions is significant for achieving bioinspired artificial intelligence. It is challenging to fabricate stimuli-responsive hydrogels showing simultaneous changes in fluorescence color, brightness, and shape in response to a single stimulus. Herein, a bilayer hydrogel strategy is designed by utilizing an aggregation-induced emission luminogen, tetra-(4-pyridylphenyl)ethylene (TPE-4Py), to fabricate hydrogels with the above capabilities. Bilayer hydrogel actuators with the ionomer of poly(acrylamide-r-sodium 4-styrenesulfonate) (PAS) as a matrix of both active and passive layers and TPE-4Py as the core function element in the active layer are prepared. At acidic pH, the protonation of TPE-4Py leads to fluorescence color and brightness changes of the actuators and the electrostatic interactions between the protonated TPE-4Py and benzenesulfonate groups of the PAS chains in the active layer cause the actuators to deform. The proposed TPE-4Py/PAS-based bilayer hydrogel actuators with such responsiveness to stimulus provide insights in the design of intelligent systems and are highly attractive material candidates in the fields of 3D/4D printing, soft robots, and smart wearable devices.
关键词： stimuli-responsive hydrogels,complex shape,simultaneous changes,fluorescence,aggregation-induced emission luminogens
更新于2025-09-19 17:13:59
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Towards Blue AIE/AIEE: Synthesis and Applications in OLEDs of Tetra-/Triphenylethenyl Substituted 9,9-Dimethylacridine Derivatives
摘要： Aiming to design blue fluorescent emitters with high photoluminescence quantum yields in solid-state, nitrogen-containing heteroaromatic 9,9-dimethylacridine was refined by tetraphenylethene and triphenylethene. Six tetra-/triphenylethene-substituted 9,9-dimethylacridines were synthesized by the Buchwald-Hartwig method with relatively high yields. Showing effects of substitution patterns, all emitters demonstrated high fluorescence quantum yields of 26–53% in non-doped films and 52–88% in doped films due to the aggregation induced/enhanced emission (AIE/AIEE) phenomena. In solid-state, the emitters emitted blue (451–481 nm) without doping and deep-blue (438–445 nm) with doping while greenish-yellow emission was detected for two compounds with additionally attached cyano-groups. The ionization potentials of the derivatives were found to be in the relatively wide range of 5.43–5.81 eV since cyano-groups were used in their design. Possible applications of the emitters were demonstrated in non-doped and doped organic light-emitting diodes with up to 2.3 % external quantum efficiencies for simple fluorescent devices. In the best case, deep-blue electroluminescence with chromaticity coordinates of (0.16, 0.10) was close to blue color standard (0.14, 0.08) of the National Television System Committee.
关键词： aggregation induced emission enhancement,electroluminescence,tetra-/triphenylethene,acridan
更新于2025-09-19 17:13:59
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Self-Assembled Extended ??-Systems for Sensing and Security Applications
摘要： Molecules and materials derived from self-assembled extended π-systems have strong and reversible optical properties, which can be modulated with external stimuli such as temperature, mechanical stress, ions, the polarity of the medium, and so on. In many cases, absorption and emission responses of self-assembled supramolecular π-systems are manifested several times higher when compared with the individual molecular building blocks. These properties of molecular assemblies encourage scientists to have a deeper understanding of their design to explore them for suitable optoelectronic applications. Therefore, it is important to bring in highly responsive optical features in π-systems, for which it is necessary to modify their structures by varying the conjugation length and by introducing donor?acceptor functional groups. Using noncovalent forces, π-systems can be put together to form assemblies of different shapes and sizes with varied optical band gaps through controlling intermolecular electronic interactions. In addition, using directional forces, it is possible to bring anisotropy to the self-assembled nanostructures, facilitating efficient exciton migration, resulting in the modulation of optical and electron-transport properties. In this Account, we mainly summarize our findings with optically tunable self-assemblies of extended π-systems such as p-phenylenevinylenes (PVs), p-phenyleneethynylenes (PEs), and diketopyrrolopyrroles (DPPs) as different stimuli-responsive platforms to develop sensors and security materials. We start with how PV self-assemblies and their coassemblies with appropriate electron-deficient systems can be used for the sensing of analytes in contact mode or in the vapor phase. For example, whereas the PV having electron-deficient terminal groups has high sensitivity toward trinitrotoluene (TNT) in contact mode, the supercoiled fibers formed by the coassembly of self-sorted stacks of C3-symmetrical PV and C3-symmetrical electron-deficient perylene bisimide are capable of sensing vapors of nitrobenzene and o-toluidine. The power of different functional groups in combination with PVs has been further illustrated by attaching CO2-sensitive tertiary amine moieties to a cyano-substituted PV, which allowed the bimodal detection of CO2 using fluorescence and Raman spectroscopy. Interestingly, the functionalization of PVs with terminal amide groups and chiral alkoxy side chains provided a mechanochromic system that allows self-erasable imaging. Whereas PVs exhibit quenching of fluorescence in most cases during self-assembly, PE derivatives exhibit aggregation-induced emission. This property of PEs has been exploited for the development of stimuli-responsive security materials, especially for currency and documents. For instance, the blue fluorescence of a PE attached to hydrophilic oxyethylene side chains coated on a filter paper upon contact with water changes to cyan emission due to the change in the molecular packing. Interestingly, the molecular packing of a Bodipy-attached PE-based gelator allowed a stress-induced change in the emission behavior, resulting in strong near-infrared (NIR) emission upon the application of mechanical stress or gelation. Finally, the use of DPP-based π-systems for the development of NIR transparent optical filters that block UV?vis light and their security- and forensic-related applications are described. These selected examples of the π-system self-assemblies provide an idea of the current status and future opportunities for scientists interested in this field of self-assembly and soft materials research.
关键词： self-assembly,sensors,π-systems,NIR transparent optical filters,stimuli-responsive,mechanochromism,fluorescence,security materials,aggregation-induced emission
更新于2025-09-19 17:13:59