Dynamic Transition between Monomer and Excimer Phosphorescence in Organic Near-Infrared Phosphorescent Crystals.

Achieving efficient near-infrared room-temperature phosphorescence of purely organic phosphors remains scarce and challenging due to strong nonradiative decay. Additionally, the investigation of triplet excimer phosphorescence is rarely reported, despite the fact that excimer, a special emitter commonly formed in crystals with strong π-π interactions, can efficiently change the fluorescent properties of compounds. Herein, a series of dithienopyrrole derivatives with low triplet energy levels and stable triplet states, exhibiting persistent near-infrared room-temperature phosphorescence, is developed. Via the modification of halogen atoms, the crystals display tunable emissions of monomers from 645 to 702 nm, with a maximum lifetime of 3.68 ms under ambient conditions. Notably, excimer phosphorescence can be switched on at low temperatures, enabled by noncovalent interactions rigidifying the matrix and stabilizing triplet excimer. Unprecedentedly, the dynamic transition process is captured between the monomer and excimer phosphorescence with temperature variations, revealing that the unstable triplet excimers in crystals with a tendency to dissociate can result in the effective quench of room-temperature phosphorescence. Excited state transitions across varying environments are elucidated, interpreting the structural dynamics of the triplet excimer and demonstrating strategies for devising novel near-infrared phosphors.

Aggregation-Induced Emission (AIE), Life and Health.

Light has profoundly impacted modern medicine and healthcare, with numerous luminescent agents and imaging techniques currently being used to assess health and treat diseases. As an emerging concept in luminescence, aggregation-induced emission (AIE) has shown great potential in biological applications due to its advantages in terms of brightness, biocompatibility, photostability, and positive correlation with concentration. This review provides a comprehensive summary of AIE luminogens applied in imaging of biological structure and dynamic physiological processes, disease diagnosis and treatment, and detection and monitoring of specific analytes, followed by representative works. Discussions on critical issues and perspectives on future directions are also included. This review aims to stimulate the interest of researchers from different fields, including chemistry, biology, materials science, medicine, etc., thus promoting the development of AIE in the fields of life and health.

Chromene-based BioAIEgens: 'in-water' synthesis, regiostructure-dependent fluorescence and ER-specific imaging.

Exploration of artificial aggregation-induced emission luminogens (AIEgens) has garnered extensive interest in the past two decades. In particular, AIEgens possessing natural characteristics (BioAIEgens) have received more attention recently due to the advantages of biocompatibility, sustainability and renewability. However, the extremely limited number of BioAIEgens extracted from natural sources have retarded their development. Herein, a new class of BioAIEgens based on the natural scaffold of chromene have been facilely synthesized via green reactions in a water system. These compounds show regiostructure-, polymorphism- and substituent-dependent fluorescence, which clearly illustrates the close relationship between the macroscopic properties and hierarchical structure of aggregates. Due to the superior biocompatibility of the natural scaffold, chromene-based BioAIEgens can specifically target the endoplasmic reticulum (ER) via the introduction of tosyl amide. This work has provided a new chromene scaffold for functional BioAIEgens on the basis of green and sustainable 'in-water' synthesis, applicable regiostructure-dependent fluorescence, and effective ER-specific imaging.

Fluorescence ratiometric assay for discriminating GSH and Cys based on the composites of UiO-66-NH2 and Cu nanoclusters.

The discriminative detection of glutathione (GSH) from cysteine (Cys) remains a challenge because of their similarity in structure and chemical properties. This study reported a strategy for selective and sensitive detection of GSH based on the GSH-promoted blue fluorescence of UiO-66-NH2 and aggregation-enhanced emission (AEE) feature of orange emissive Cu nanoclusters (NCs). A relatively weak blue fluorescence of UiO-66-NH2 was converted to strong after reacting with GSH due to the rotation-restricted emission enhancement mechanism. In addition, the GSH-activated UiO-66-NH2 was further used as a template and reducing reagent for synthesizing orange-red AEE active Cu NCs composites (UiO-66-NH2@Cu NCs). A ratiometric fluorescence response was observed after forming UiO-66-NH2@Cu NCs, helping discriminate GSH over Cys. In addition, UiO-66-NH2@Cu NCs were further utilized for the detection of GSH in clinical samples. The present findings provide an efficient strategy to discriminate GSH over Cys and open a new door for utilizing and functionalizing metal-organic frameworks (MOFs) for various applications.

Secondary through-space interactions facilitated single-molecule white-light emission from clusteroluminogens.

Clusteroluminogens refer to some non-conjugated molecules that show visible light and unique electronic properties with through-space interactions due to the formation of aggregates. Although mature and systematic theories of molecular photophysics have been developed to study conventional conjugated chromophores, it is still challenging to endow clusteroluminogens with designed photophysical properties by manipulating through-space interactions. Herein, three clusteroluminogens with non-conjugated donor-acceptor structures and different halide substituents are designed and synthesized. These compounds show multiple emissions and even single-molecule white-light emission in the crystalline state. The intensity ratio of these emissions is easily manipulated by changing the halide atom and excitation wavelength. Experimental and theoretical results successfully disclose the electronic nature of these multiple emissions: through-space conjugation for short-wavelength fluorescence, through-space charge transfer based on secondary through-space interactions for long-wavelength fluorescence, and room-temperature phosphorescence. The introduction of secondary through-space interactions to clusteroluminogens not only enriches their varieties of photophysical properties but also inspires the establishment of novel aggregate photophysics for clusteroluminescence.

Organic Long-Persistent Luminescence from a Single-Component Aggregate.

Long-persistent luminescence (LPL), also known as afterglow, is a phenomenon in which the material shows long-lasting luminescence after the cessation of the excitation source. The research of LPL continues to attract much interest due to its fundamental nature and its potential in the development of the next generation of functional materials. However, most of the current LPL materials are multicomponent inorganic systems obtained after harsh synthetic procedures and often use rare-earth metals. Recently, metal free organic long-persistent luminescence (OLPL) has gained much interest because it can bypass many of the disadvantages of inorganic systems. To date, the most successful method to generate OLPL systems is to access charge-separated states through binary donor-acceptor exciplex systems. However, it has been reported that the ratios of the binary systems affect OLPL properties, complicating the reproducibility and large-scale production of OLPL materials. Simpler OLPL systems can overcome these issues for the benefit of the development and adoption of OLPL systems. Here, we report on the rational design and synthesis of a single-component OLPL system with detectable afterglow for at least 12 min under ambient conditions. This work exemplifies an easy design principle for new OLPL materials. The investigation of the material provides valuable insights toward the generation of OLPL from a single-component system.

Phototriggered Aggregation-Induced Emission and Direct Generation of 4D Soft Patterns.

Microscopic control of macroscopic phenomena is one of the core subjects in materials science. Particularly, the spatio-temporal control of material behaviors through a non-contact way is of fundamental importance but is difficult to accomplish. Herein, a strategy to realize remote spatio-temporal control of luminescence behaviors is reported. A multi-arm salicylaldehyde benzoylhydrazone-based aggregation-induced emission luminogen (AIEgen)/metal-ion system, of which the fluorescence can be gated by the UV irradiation with time dependency, is developed. By changing the metal-ion species, the fluorescence emission and the intensity can also be tuned. The mechanism of the UV-mediated fluorescence change is investigated, and it is revealed that a phototriggered aggregation-induced emission (PTAIE) process contributes to the behaviors. The AIEgen is further covalently integrated into a polymeric network and the formed gel/metal-ion system can achieve laser-mediated mask-free writing enabled by the PTAIE process. Moreover, by further taking advantage of the time-dependent self-healing property of hydrazone-based dynamic covalent bond, transformable 4D soft patterns are generated. The findings and the strategy increase the ways to manipulate molecules on the supramolecule or aggregate level. They also show opportunities for the development of controllable smart materials and expand the scope of the materials in advanced optoelectronic applications.

Origin of Intense Luminescence from Supramolecular 2D Molecular Crystals.

Luminescence enhancement in 2D molecular crystals (2D crystals) is promising for a variety of optical applications, yet the availability is limited because of unclear mechanism and inefficient design strategy of luminescence control. Herein, the room temperature phosphorescence from micron long molecular thin free-standing 2D crystals of a mono-cyclometalated Ir(III) complex designed at the water surface is reported. A large luminescence enhancement is observed from the 2D crystals at 300 K, which is comparable with the rigidified solution at 77 K suggesting room temperature phosphorescence origin of the luminescence. In situ synchrotron grazing incidence X-ray diffraction measurements determine the constituent centered rectangular unit cells with precise molecular conformation that promotes the formation of 2D crystals. The molecular crystal design leads to a reduced singlet-triplet energy gap (ΔEST ) and mixing of singlet-triplet states by spin-orbit coupling (SOC) for efficient intersystem crossing, which explains the phosphorescence origin at room temperature and luminescence enhancement. The supramolecular assembly process provides an elegant design strategy to realize room temperature phosphorescence from 2D crystals by rigid intermolecular interactions.

Stimuli-Responsive AIEgens.

The unique advantages and the exciting application prospects of AIEgens have triggered booming developments in this area in recent years. Among them, stimuli-responsive AIEgens have received particular attention and impressive progress, and they have been demonstrated to show tremendous potential in many fields from physical chemistry to materials science and to biology and medicine. Here, the recent achievements of stimuli-responsive AIEgens in terms of seven most representative types of stimuli including force, light, polarity, temperature, electricity, ion, and pH, are summarized. Based on typical examples, it is illustrated how each type of systems realize the desired stimuli-responsive performance for various applications. The key work principles behind them are ultimately deciphered and figured out to offer new insights and guidelines for the design and engineering of the next-generation stimuli-responsive luminescent materials for more broad applications.

Hydrazine Detection during Ammonia Electro-oxidation Using an Aggregation-Induced Emission Dye.

Ammonia electro-oxidation is an extremely significant reaction with regards to the nitrogen cycle, hydrogen economy, and wastewater remediation. The design of efficient electrocatalysts for use in the ammonia electro-oxidation reaction (AOR) requires comprehensive understanding of the mechanism and intermediates involved. In this study, aggregation-induced emission (AIE), a robust fluorescence sensing platform, is employed for the sensitive and qualitative detection of hydrazine (N2H4), one of the important intermediates during the AOR. Here, we successfully identified N2H4 as a main intermediate during the AOR on the model Pt/C electrocatalyst using 4-(1,2,2-triphenylvinyl)benzaldehyde (TPE-CHO), an aggregation-induced emission luminogen (AIEgen). We propose the AOR mechanism for Pt with N2H4 being formed during the dimerization process (NH2 coupling) within the framework of the Gerischer and Mauerer mechanism. The unique chemodosimeter approach demonstrated in this study opens a novel pathway for understanding electrochemical reactions in depth.

Molecular Motions in AIEgen Crystals: Turning on Photoluminescence by Force-Induced Filament Sliding.

Life process is amazing, and it proceeds against the eternal law of entropy increase through molecular motion and takes energy from the environment to build high-order complexity from chaos to achieve evolution with more sophisticated architectures. Inspired from the elegance of life process and also to effectively exploit the undeveloped solid-state molecular motion, two unique chiral Au(I) complexes were elaborately developed in this study, in which their powders could realize a dramatic transformation from nonemissive isolated crystallites to emissive well-defined microcrystals under the stimulation of mechanical force. Such an unusual crystallization was presumed to be caused by molecular motions driven by the formation of strong aurophilic interactions as well as multiple C-H···F and π-π interactions. Such a prominent macroscopic off/on luminescent switching could also be achieved through extremely subtle molecular motions in the crystal state and presented a filament sliding that occurred in a layer-by-layer molecular stacking fashion with no involvement of any crystal phase transition. Additionally, it had been demonstrated that the manipulation of the solid-state molecular motions could result in the generation of circularly polarized luminescence.

Melatonin modulates photosynthesis, redox status, and elemental composition to promote growth of Brassica juncea-a dose-dependent effect.

Melatonin (MEL) is an antioxidant molecule, present throughout plant kingdom, animals, and microbes. It is a well-known free radical scavenger and modulates growth and development in plants against various abiotic and biotic stresses. The present study was done to investigate the role of MEL as a foliar spray on the morphological, physiological, and biochemical parameters in Brassica juncea cv. Varuna. Five different doses (10, 20, 30, 40, or 50 µM) of MEL were applied as foliar spray to the leaf of plant at 25 days after sowing (DAS) and continued up to 30 DAS once in a day. The plants were sampled at 30, 45, and 60 DAS to assess various parameters. The present results indicate that most of the parameters, i.e., growth, photosynthetic, nutrients, and enzyme activities increased in a concentration dependent manner. MEL application reduced the accumulation of reactive oxygen species (ROS) by enhancing the antioxidant enzyme activities. Microscopic examinations further revealed a significant increase in the size of the stomatal aperture in the presence of MEL. Out of the various concentrations tested, 40 µM of MEL proved best and can be used for further studies.

Semi-quantitative evaluation of seafood spoilage using filter-paper strips loaded with an aggregation-induced emission luminogen.

The method for seafood spoilage detection is far from satisfactory for ensuring food safety and security. Here, we develop a simple and cost-effective method using the filter papers loaded with a dihydroquinoxaline derivative (H + DQ2) to monitor salmon spoilage. The correlation between the content of solid biogenic amines and the photoluminescence intensity (PL) of H + DQ2 induced by amine vapours showed that the PL intensities of H + DQ2 increased with the increase of spoilage, which indicates that it is feasible to evaluate the spoilage degree of salmon based on the PL intensity of H + DQ2-loaded filter papers by semi-quantitation. The optimum detection condition is 75, 50 and 50 g of salmon, 75, 25 and 10 µM H + DQ2 at 0, 4 and 25 °C, respectively. This study provides a quick and simple way for testing amine vapour from fish and provides baseline information for developing an easy-to-use on-site method to evaluate seafood quality for customers.

Two Are Better Than One: A Design Principle for Ultralong-Persistent Luminescence of Pure Organics.

Because of their innate ability to store and then release energy, long-persistent luminescence (LPL) materials have garnered strong research interest in a wide range of multidisciplinary fields, such as biomedical sciences, theranostics, and photonic devices. Although many inorganic LPL systems with afterglow durations of up to hours and days have been reported, organic systems have had difficulties reaching similar timescales. In this work, a design principle based on the successes of inorganic systems to produce an organic LPL (OLPL) system through the use of a strong organic electron trap is proposed. The resulting system generates detectable afterglow for up to 7 h, significantly longer than any other reported OLPL system. The design strategy demonstrates an easy methodology to develop organic long-persistent phosphors, opening the door to new OLPL materials.

Ultralong UV/mechano-excited room temperature phosphorescence from purely organic cluster excitons.

Purely organic room temperature phosphorescence (RTP) has attracted wide attention recently due to its various application potentials. However, ultralong RTP (URTP) with high efficiency is still rarely achieved. Herein, by dissolving 1,8-naphthalic anhydride in certain organic solid hosts, URTP with a lifetime of over 600 ms and overall quantum yield of over 20% is realized. Meanwhile, the URTP can also be achieved by mechanical excitation when the host is mechanoluminescent. Femtosecond transient absorption studies reveal that intersystem crossing of the host is accelerated substantially in the presence of a trace amount of 1,8-naphthalic anhydride. Accordingly, we propose that a cluster exciton spanning the host and guest forms as a transient state before the guest acts as an energy trap for the RTP state. The cluster exciton model proposed here is expected to help expand the varieties of purely organic URTP materials based on an advanced understanding of guest/host combinations.

Spontaneous and Fast Molecular Motion at Room Temperature in the Solid State.

The development of molecular machines requires new building blocks which are easy to characterize and visualize to realize a complexity comparable to their natural counterparts such as biological enzymes. Furthermore, with the desire to build functional nanobots capable of navigating living organisms, it is necessary that the building blocks show mobility even in the solid state. Herein we report a system which is emissive in the amorphous state but is non-fluorescent in the crystalline state due to the formation of extensive π-π interactions. This dual nature could be exploited for easy visualization of its solid-state molecular rearrangement. The emission of the amorphous film was quenched as the molecules spontaneously formed π-π interactions even in the solid state. Scratching the non-emissive film destroyed the interactions and restored the emission of the film. The emission quickly disappeared with an average lifetime of 20 s as the compound reformed the π-network even at room temperature.

A Highly Sensitive Bimodal Detection of Amine Vapours Based on Aggregation Induced Emission of 1,2-Dihydroquinoxaline Derivatives.

The detection of food spoilage is a major concern in food safety as large amounts of food are transported globally. Direct analysis of food samples is often time-consuming and requires expensive analytical instrumentation. A much simpler and more cost-effective method for monitoring food fermentation is to detect biogenic amines generated as a by-product during food decomposition. In this work, a series of 1,2-dihydroquinoxaline derivatives (DQs) with aggregation-induced emission (AIE) characteristics were synthesised and their protonated forms, that is, H+ DQs, can be utilised for the sensitive detection of biogenic amines. For example, upon exposure to amine vapours, deprotonation occurs that converts the red-coloured, non-emissive H+ DQ2 back to its yellow-coloured, fluorescent parent form. The bimodal absorption and emission changes endow the system with high sensitivity, capable of detecting ammonia vapour at a concentration of as low as 690 ppb. Taking advantage of this, H+ DQ2 was successfully applied for the detection of food spoilage and was established as a robust and cost effective technique to monitor food safety.

Induced Aggregation of AIE-Active Mono-Cyclometalated Ir(III) Complex into Supramolecular Branched Wires for Light-Emitting Diodes.

Aggregation-induced emission (AIE) is commonly observed in irregular bulk form. Herein, unique aggregation properties of an AIE-active complex into branched supramolecular wires are reported for the first time. Mono-cyclometalated Ir(III) complex shows in-plane J-aggregation at the air-water interface owing to the restriction of intramolecular vibration of bidentate phenylpyridinato and intramolecular rotations of monodentate triphenylphosphine ligands at air-water interface. As a consequence, a large enhancement of luminescence comparable to the solid state is obtained from the monolayers of supramolecular wires. This unique feature is utilized for the fabrication of light-emitting diodes with low threshold voltage using supramolecular wires as active layer. This study opens up the need of ordered assembly of AIE complexes to achieve optimal luminescence characteristics.

"Aggregation induced phosphorescence" active "rollover" iridium(III) complex as a multi-stimuli-responsive luminescence material.

On reaction of 2,2'-bipyridine with iridium(iii), an "aggregation induced phosphorescence (AIP)" active "rollover" complex, [Ir(PPh3)2(bipy-H)(Cl)(H)] (bipy-H = κ(2)-N,C-2,2'-bipyridine) or [Ir(bipy-H)], is obtained. The emission colour changes from bluish-green to yellowish-orange and vice versa after repeated protonation and deprotonation of [Ir(bipy-H)], respectively, which unequivocally supports its reversible nature. [Ir(bipy-H)] is sensitive to acids with different pKa values. Tuning of the emission properties can be achieved in the presence of acids with different pKas. This behaviour allows the complex, [Ir(bipy-H)], to function as a phosphorescent acid sensor in both solution and the solid state, as well as a chemosensor for detecting acidic and basic organic vapours. The protonated form, [Ir(bipy-H)H(+)], which is generated after protonation of [Ir(bipy-H)] can be used as a solvatochromic probe for oxygen containing solvents, and also shows vapochromic properties. The emission, absorption and (1)H NMR spectra of [Ir(bipy-H)] under acidic and basic conditions demonstrate its reversible nature. DFT based calculations suggest that changes in the electron affinity of the pyridinyl rings are responsible for all these processes.

New 'aggregation induced emission (AIE)' active cyclometalated iridium(III) based phosphorescent sensors: high sensitivity for mercury(II) ions.

Design and syntheses of 'aggregation induced emission (AIE)' active blue-emitting bis-cyclometalated iridium(III) complexes with appended diphosphine ligands [Ir(F2ppy)2(L1/L2)2(Cl)] (F2ppy = 2-(2',4'-difluoro) phenylpyridine; L1 = 1,2-bis(diphenylphosphino)ethane; L2 = bis(diphenylphosphino)propane) have been realized on a suitable route. The free phosphorous donor atom present on the appended diphosphine is shown to provide selective binding to the mercuric ion (Hg(2+)). The selective binding ability of the probe molecule towards mercuric ions results in a detectable signal due to complete quenching of their AIE properties. The quenching effect of the probe molecule has been explored and found to be the result of the degradation of the probe iridium(III) complex triggered by the presence of mercuric ions due to an interplay of a soft-soft interaction between the free phosphorous atom of the probe molecule and mercuric ions. These complexes were modelled to obtain deeper understanding of excited state properties and the results were tentatively correlated with the experimental data.