Hierarchical Dual-Mode Efficient Tunable Afterglow via J-Aggregates in Single-Phosphor-Doped Polymer.

The development of polymer-based persistent luminescence materials with color-tunable organic afterglow and multiple responses is highly desirable for the applications in anti-counterfeiting, flexible displays and data-storage. However, achieving efficient persistent luminescence from a single-phosphor system with multiple responses remains a challenging task. Herein, a hierarchical dual-mode emission system is developed by doping 9H-pyrido[3,4-b]indole (PI2) into an amorphous polyacrylamide matrix, which exhibits color-tunable afterglow due to excitation-, temperature- and humidity-dependence. Notably, the coexistence of isolated state and J-aggregate state of the guest molecule not only provides excitation-dependent afterglow color, but also leads to hierarchical temperature-dependent afterglow color resulting from different thermally activated delayed fluorescence (TADF) and ultralong organic phosphorescence (UOP) behaviors of the isolated and aggregated states. The complex responsiveness based on the hierarchical dual-mode emission can serve for security features through inkjet printing and ink-writing. These findings may provide further insight into the regulated persistent luminescence by isolated and aggregated phosphors in doped polymer systems and expand the scope of stimuli-responsive organic afterglow materials for broader applications.

Dynamic Ultra-long Room Temperature Phosphorescence Enabled by Amorphous Molecular "Triplet Exciton Pump" for Encryption with Temporospatial Resolution.

Organic ultra-long room-temperature phosphorescence (RTP) materials in the amorphous state have attracted widespread attention due to their simple preparation and flexibility to adopt various forms in sensors, bioimaging, and encryption applications. However, the amorphous molecular host for the host-guest RTP systems is highly demanded but limited. Here, a universal molecular host (DPOBP-Br) has been designed by integration of an amorphous moiety of diphenylphosphine oxide (DPO) and an intersystem crossing (ISC) group of 4-bromo-benzophenone (BP-Br). Various commercial fluorescence dyes were doped into the tight and transparent DPOBP-Br film, respectively, resulting in amorphous host-guest systems with ultra-long RTP colors from green to red. It was found that DPOBP-Br acted as a universal "triplet exciton pump" for promoting the generation of triplet excitons in the guest, through energy transfer processes and external heavy-atom effect based on DPOBP-Br. Interestingly, dynamic RTP was achieved by controlling residual oxygen concentration in the amorphous matrix by UV irradiation. Therefore, multi-dimensional anti-counterfeiting coatings were realized even on curved surfaces, simultaneously exhibiting spatial and 2D-time dependence. This work provides a strategy to design new amorphous molecular hosts for RTP systems and demonstrates the advanced information encryption with tempo-spatial resolution based on the dynamic ultra-long RTP of an amorphous system.

Achieving Record External Quantum Efficiency of 11.5 % in Solution-Processable Deep-Blue Organic Light-Emitting Diodes Utilizing Hot Exciton Mechanism.

High performance solution-processable deep-blue emitters with a Commission International de l'Eclairage (CIE) coordinate of CIEy≤0.08 are highly desired in ultrahigh-definition display. Although, deep-blue materials with hybridized local and charge-transfer (HLCT) excited-state feature are promising candidates, their rigidity and planar molecular structures limit their application in solution-processing technique. Herein, four novel deep-blue solution-processable HLCT emitters were first proposed by attaching rigid imide aliphatic rings as functional units onto the HLCT emitting core. The functional units not only improve solubility, enhance thermal properties and morphological stability of the emitting core, but also promote photoluminescence efficiency, balance charge carrier transport, and inhibit aggregation-caused quenching effect due to the weak electron-withdrawing property as well as steric hindrance. The corresponding solution-processable organic light-emitting diodes (OLEDs) substantiate an unprecedented maximum external quantum efficiency (EQEmax) of 11.5 % with an emission peak at 456 nm and excellent colour purity (full width at half maximum=56 nm and CIEy=0.09). These efficiencies represent the state-of-the-art device performance among the solution-processable blue OLEDs based on the "hot exciton" mechanism. This simple strategy opens up a new avenue for designing highly efficient solution-processable deep-blue organic luminescent materials.

Enabling Highly Robust Full-Color Ultralong Room-Temperature Phosphorescence and Stable White Organic Afterglow from Polycyclic Aromatic Hydrocarbons.

In this work, full-color and stable white organic afterglow materials with outstanding water, organic solvents, and temperature resistances have been developed for the first time by embedding the selected polycyclic aromatic hydrocarbons into melamine-formaldehyde polymer via solution polymerization. The afterglow quantum yields and lifetimes of the resulting polymer films were up to 22.7 % and 4.83 s, respectively, under ambient conditions. For the coronene-doped sample, its afterglow color could be linearly tuned between yellow and blue by adjusting the temperature, and it could still emit an intense blue afterglow with a lifetime of 0.68 s at 440 K. Moreover, the films showed a bright and stable white afterglow at 370 K with a lifetime of 2.80 s and maintained an excellent afterglow performance after soaking in water and organic solvents for more than 150 days. In addition, the application potential of the polymer films in information encryption and anti-counterfeiting was also demonstrated.

Synergetic Conformational Regulations in Ground and Excited States for Realizing Stimulus-Responsive and Wide-Tuning Room-Temperature Phosphorescence.

Understanding the changes of molecular conformations is crucial for realizing multiple emissive triplet states in room-temperature phosphorescence (RTP) materials. In this work, we report two molecules, 4,4'-dimethylbenzil (DMBZ) and 4,4'-di-tert-butylbenzil (DBBZ) with conformation-dependent luminescence, and demonstrate that stimulus-responsive and wide-tuning RTP emissions can be realized via synergetic conformational regulations in ground and excited states. Due to conformational changes, DMBZ and DBBZ show abundant RTP variations upon external stimuli, including light, force, heat, and fumigation. Notably, DBBZ exhibits multiple conformational changes in both ground and excited states, which endow DBBZ with multiple emissive states and unique stimulus-responsive behaviors. DBBZ presents multiple phase transitions between the supercooled liquid state and different solid states accompanied by different phosphorescence transitions, in which the excited-state conformations are effectively regulated. Moreover, wide-range RTP regulations (between cyan, green, and yellow) are realized in both single component and host-guest systems of DBBZ, showing potential applications in temperature sensing, multicolor dynamic displays, and information encryption. These results may provide new visions for understanding the complicated conformational changes in the aggregated state, as well as unique insights into the relationship between molecular conformations, RTP emissions, and stimulus responsiveness.

Y-Shaped D-A Type Thioxanthone Derivatives: Mechano-Induced Thermally Activated Delayed Fluorescence and High-Contrast Mechano-Responsive Luminescence.

High-contrast mechano-responsive luminescence (MRL) materials with mechano-induced emission enhancement properties are fascinating candidates but few, for applications in rewritable media and recording devices. Here, an interesting design strategy of "Y-shape" donor-acceptor (D-A) type molecules for high-contrast MRL materials was presented, based on substituted diphenylamine donor and planar acceptor. Interestingly, their D-A torsion angles are small in crystals but increased after ground, resulted in planar and twist intramolecular charge transfer (PICT and TICT) states, respectively. Therefore, high-contrast MRL switching between weak blue (450 nm) fluorescence and bright yellow (552 nm) thermally activated delayed fluorescence (TADF) can be achieved for compound TXDO (4,4'-dimethoxydiphenylamine donor), which photoluminescence quantum yield increased from 2.8 % to 54.7 % after ground. Most importantly, the two independent D-A conjugation dihedral angles are actually independent in the "Y-shape" molecules. Especially for compound TXDT (4,4'-di-tert-butyldiphenylamine donor), its crystal exhibited both PICT and TICT processes inside, resulted from the different dihedral angles of 11.8° and 35.5°, respectively. The TXDT crystal thus showed dual-peak emission, including both TICT fluorescence and PICT room-temperature phosphorescence. Therefore, this strategy of "Y-shape" D-A type molecules provide a new approach to design advanced luminescent materials with mechano-induced TADF feature, for high-contrast MRL and single-component white luminescence.

Multistimuli-responsive fluorescence behaviours of aggregation-induced emission small-molecule and electrospun nanofibre films for acid-base vapour sensing.

Multistimuli-responsive fluorescent materials have garnered great research interest benefited from their practical applications. Two twisted-structure compounds containing tetraphenylethylene (TPE) as the aggregation-induced emission (AIE) group and a pyridine unit as the acid reaction site to obtain new multistimuli-responsive fluorescent compounds (namely, TPECNPy: TPECNPy-2 and TPECNPy-3) were successfully synthesized through a one-step Knoevenagel condensation reaction. The multiple-stimuli response process of TPECNPy was investigated by means of photoluminescence (PL) spectra and emission colour. The results showed that both TPECNPy compounds with excellent AIE abilities displayed reversible emission wavelength and colour changes in response to multiple external stimuli, including grinding-fuming by CH2 Cl2 or annealing and HCl-NH3 vapour fuming. More importantly, fluorescent nanofibre films were prepared by electrospinning a solution of TPECNPy mixed with cellulose acetate (CA), and these exhibited reversible acid-induced discolouration, even with only 1 wt% TPECNPy. The results of this study may inspire strategies for designing multistimuli-responsive materials and preparing fluorescent sensing nanofibre films.

Color-Tunable Dual-Mode Organic Afterglow from Classical Aggregation-Caused Quenching Compounds for White-Light-Manipulated Anti-Counterfeiting.

Color-tunable dual-mode organic afterglow excited by ultraviolet (UV) and white light was achieved from classical aggregation-caused quenching compounds for the first time. Specifically, two luminescent systems, which could produce significant organic afterglow composed of persistent thermally activated delayed fluorescence and ultralong organic phosphorescence under ambient conditions, were constructed by doping fluorescein sodium and calcein sodium into aluminum sulfate. Their lifetimes surpassed 600 ms, and the dopant concentrations were as low as 5×10-6  wt %. Moreover, the persistent luminescence colors of the materials could be tuned from blue to green and then to yellow by simply varying the concentrations of guest compounds or the temperature in the range of 260-340 K. Inspired by these exciting results, the afterglow materials were used for UV- and white-light-manipulated anti-counterfeiting and preparation of elastomers with different colors of persistent luminescence.

Carbazole isomers induce ultralong organic phosphorescence.

Commercial carbazole has been widely used to synthesize organic functional materials that have led to recent breakthroughs in ultralong organic phosphorescence1, thermally activated delayed fluorescence2,3, organic luminescent radicals4 and organic semiconductor lasers5. However, the impact of low-concentration isomeric impurities present within commercial batches on the properties of the synthesized molecules requires further analysis. Here, we have synthesized highly pure carbazole and observed that its fluorescence is blueshifted by 54 nm with respect to commercial samples and its room-temperature ultralong phosphorescence almost disappears6. We discover that such differences are due to the presence of a carbazole isomeric impurity in commercial carbazole sources, with concentrations <0.5 mol%. Ten representative carbazole derivatives synthesized from the highly pure carbazole failed to show the ultralong phosphorescence reported in the literature1,7-15. However, the phosphorescence was recovered by adding 0.1 mol% isomers, which act as charge traps. Investigating the role of the isomers may therefore provide alternative insights into the mechanisms behind ultralong organic phosphorescence1,6-18.

Temperature-Resistant Intrinsic High Dielectric Constant Polyimides: More Flexibility of the Dipoles, Larger Permittivity of the Materials.

High dielectric constant polymers have been widely studied and concerned in modern industry, and the induction of polar groups has been confirmed to be effective for high permittivity. However, the way of connection of polar groups with the polymer backbone and the mechanism of their effect on the dielectric properties are unclear and rarely reported. In this study, three polyimides (C0-SPI, C1-SPI, and C2-SPI) with the same rigid backbone and different linking groups to the dipoles were designed and synthesized. With their rigid structure, all of the polyimides show excellent thermal stability. With the increase in the flexibility of linking groups, the dielectric constant of C0-SPI, C1-SPI, and C2-SPI enhanced in turn, showing values of 5.6, 6.0, and 6.5 at 100 Hz, respectively. Further studies have shown that the flexibility of polar groups affected the dipole polarization, which was positively related to the dielectric constant. Based on their high permittivity and high temperature resistance, the polyimides exhibited outstanding energy storage capacity even at 200 °C. This discovery reveals the behavior of the dipoles in polymers, providing an effective strategy for the design of high dielectric constant materials.

Synergistic Generation and Accumulation of Triplet Excitons for Efficient Ultralong Organic Phosphorescence.

The traditional method to achieve ultralong organic phosphorescence (UOP) is to hybrid nπ* and ππ* configurations in appropriate proportion, which are contradictory to each other for improving efficiency and lifetime of phosphorescence. In this work, through replacing the electron-donating aromatic group with a methoxy group and combining intramolecular halogen bond to promote intersystem crossing and suppress non-radiative transition, an efficient UOP molecule (2Br-OSPh) has been synthesized with the longest lifetime and brightest UOP among its isomers. As compared to CzS2Br, which has a similar substituted position of bromine atom and a larger kisc (the rate of intersystem crossing), the smaller ΔETT* (the energy gap between monomeric phosphorescence and aggregated state phosphorescence) in 2Br-OSPh could accelerate the transition from T1 to T1 *. This research indicates that both generation and accumulation of triplet excitons play an important role in realizing efficient UOP materials.

Efficient and Color-Tunable Dual-Mode Afterglow from Large-Area and Flexible Polymer-Based Transparent Films for Anti-Counterfeiting and Information Encryption.

It remains a great challenge to develop polymer-based materials with efficient and color-tunable organic afterglow. Two indolocarbazole derivatives IaCzA and IbCzA have been synthesized and doped into poly(vinyl alcohol) (PVA) matrices. It is found that the resulting films can produce unique dual-mode afterglow, which is composed of persistent thermally activated delayed fluorescence and ultralong organic phosphorescence. Besides, the IbCzA-doped PVA film exhibits intense blue afterglow with Φafterglow and τafterglow up to 19.8 % and 1.81 s, respectively, representing state-of-the-art dual-mode organic afterglow performance. Moreover, our reported film has high flexibility, excellent transparency, and large-area producibility; and the afterglow color of the film can be linearly tuned by temperature. Inspired by these distinctive properties, the PVA doped with IbCzA was employed as temperature-sensitive security ink for anti-counterfeiting and information encryption.

An Effective Strategy of Combining Surface Passivation and Secondary Grain Growth for Highly Efficient and Stable Perovskite Solar Cells.

Interfacial engineering methods have been developed to solve defect issues of perovskite solar cells (PSCs). However, traditional surface passivation has limited effects on eliminating defect-forming residuals, while secondary grain growth (SGG) is restricted by limited choices of additives and intrinsic properties of perovskites. Here, a pincer strategy of taking advantages of surface passivation and SGG is proposed to modify both exterior and interior of CH3 NH3 PbI3 (MAPbI3 ) perovskite, by employing cyanoacetate-containing donor-acceptor compounds (CA-D-A) including 2-cyano-3-(3,4,5-trimethoxyphenyl)acrylic acid (CA), methanaminium 2-cyano-3-(3,4,5-trimethoxyphenyl)acrylate (CAMA), and aminomethaniminium (Z)-2-cyano-3-(3,4,5-trimethoxyphenyl)acrylate (CAFA). In comparison to untreated perovskite, CA-D-A treated perovskites present better crystallinity because of SGG, lower trap densities due to the synergistic effect of surface passivation and SGG, and tuned energy levels induced by CA-D-A. Accordingly, the CA-D-A treated MAPbI3 -based PSCs exhibit higher open-circuit voltage and fill factor than the control PSC without any treatment, leading to improved power conversion efficiency (PCE) and enhanced device stability, especially the CAMA treated PSCs with an average PCE promoted from 17.77 (control PSCs) to 18.71%, and importantly an excellent PCE of 19.71% through further optimization. This work provides an effective strategy for developing highly efficient and stable PSCs with the assistance of both surface passivation and SGG.

Chirality in peptide-based materials: From chirality effects to potential applications.

Chirality is ubiquitous in nature with primary cellular functions that include construction of right-/left-handed helix and selective communications among diverse biomolecules. Of particularly intriguing are the chiral peptide-based materials that can be deliberately designed to change physicochemistry properties via tuning peptide sequences. Critically, understanding their chiral effects are fundamental for the development of novel materials in chemistry and biomedicine fields. Here, we review recent researches on chirality in peptide-based materials, summarizing relevant typical chiral effects towards recognition, amplification, and induction. Driven forces for the chiral discrimination in affinity interaction as well as the handedness preferences in supramolecular structure formation at both the macroscale and microscale are illustrated. The implementation of such chirality effects of artificial copolymers, assembled aggregates and their composites in the fields of bioseparation and bioenrichment, cell incubation, protein aggregation inhibitors, chiral smart gels, and bionic electro devices are also presented. At last, the challenges in these areas and possible directions are pointed out. The diversity of chiral roles in the origin of life and chirality design in different organic or composite systems as well as their applications in drug development and chirality detection in environmental protection are discussed.

Sensitive and Repeatable Photoinduced Luminescent Radicals from A Simple Organic Crystal.

Photoinduced organic radicals are important for chemical and physical processes of organic materials, which are extensively investigated and applied in organic synthesis, photoelectronic devices and biotechnology. However, there are rare reports of the luminescence for these photoinduced radicals, especially in the condensed state. Herein, an unexpected and interesting luminescent radical is described, which can be rapidly and reversibly generated from a simple organic crystal by gentle light irradiation in air. It was revealed that the twist and asymmetric conformation of isolated molecule in its crystal with only weak C-H⋅⋅⋅π intermolecular interactions, which led to the generation of such photoinduced luminescent radicals. In addition, dual-channel photosensitive device with rapid response and well repeatability can be obtained based on the thin film of this organic crystal, showing both photoswitching on luminescence and conducting.

Rigid Polyimides with Thermally Activated Delayed Fluorescence for Polymer Light-Emitting Diodes with High External Quantum Efficiency up to 21 .

A series of rigid nonconjugated polyimide (PI)-based thermally activated delayed fluorescence (TADF) polymers were reported for the first time, based on a "TADF-Linker-Host" strategy. Among of which, the TADF unit contains a typical TADF luminous core structure, the "Host" unit exhibits effective conjugation length that endows polyimide with high triplet energy, and the "Linker" unit has an aliphatic ring structure to improve solubility and inhibits intramolecular charge transfer effect. All the TADF polymers exhibit high thermal stability (Tg >308.7 °C) and refractive index (1.76-1.79). Remarkably, highly-efficient polymer light-emitting diodes (PLEDs) based on the polymers are successfully realized, leading to a maximal external quantum efficiency of 21.0 % along with low efficiency roll-off. Such outstanding efficiency is amongst the state-of-the-art performance of nonconjugated PLEDs, confirming the effectiveness of structural design strategy, providing helpful and valuable guidance on the development of highly-efficient fluorescent polymer materials and PLEDs.

Activating Versatile Mechanoluminescence in Organic Host-Guest Crystals by Controlling Exciton Transfer.

Mechanoluminescence (ML) materials are attracting increasing interest owing to promising applications in various areas. However, to date, it remains a major challenge to develop a precise and universal route to achieving organic ML materials. Herein, we show that ML can be easily realized in organic piezophotonic host-guest crystals, under conditions in which neither the host nor the guest is ML-active. The experimental and theoretical results reveal that excitons of the host generated by piezoelectricity can be harvested effectively by the guest for light emission, owing to the restraint of intersystem crossing process. Moreover, different host-guest crystals are constructed, wherein the emission color, intensity, color purity, and emission duration of ML can be manipulated. This work deepens our understanding of organic ML generation in piezophotonic host-guest crystals and provides an inspiring principle to design more organic ML materials.

Boosting the Quantum Efficiency of Ultralong Organic Phosphorescence up to 52 % via Intramolecular Halogen Bonding.

Ultralong organic phosphorescence (UOP) has attracted increasing attention due to its potential applications in optoelectronics, bioelectronics, and security protection. However, achieving UOP with high quantum efficiency (QE) over 20 % is still full of challenges due to intersystem crossing (ISC) and fast non-radiative transitions in organic molecules. Here, we present a novel strategy to enhance the QE of UOP materials by modulating intramolecular halogen bonding via structural isomerism. The QE of CzS2Br reaches up to 52.10 %, which is the highest afterglow efficiency reported so far. The crucial reason for the extraordinary QE is intramolecular halogen bonding, which can not only effectively enhance ISC by promoting spin-orbit coupling, but also greatly confine motions of excited molecules to restrict non-radiative pathways. This work provides a reasonable strategy to develop highly efficient UOP materials for practical applications.

Selective Expression of Chromophores in a Single Molecule: Soft Organic Crystals Exhibiting Full-Colour Tunability and Dynamic Triplet-Exciton Behaviours.

Soft luminescent materials are attractive for optoelectronic applications, however, switching dominant chromophores for property enrichment remains a challenge. Herein, we report the first case of a soft organic molecule (DOS) featuring selective expression of chromophores. In response to various external stimuli, different chromophores of DOS can take turns working through conformation changes, exhibiting full-colour emissions peaking from 469 nm to 583 nm from ten individual single crystals. Dynamic triplet-exciton behaviours including thermally activated delayed fluorescence (TADF), room-temperature phosphorescence (RTP), mechanoluminescence (ML), and distinct mechano-responsive luminescence (MRL) can all be realized. This novel designed DOS molecule provides a multifunctional platform for detection of volatile organic compounds (VOCs), multicolour dynamic displays, sensing, anticounterfeiting, and hopefully many others.

Recent advances in organic thermally activated delayed fluorescence materials.

Organic materials that exhibit thermally activated delayed fluorescence (TADF) are an attractive class of functional materials that have witnessed a booming development in recent years. Since Adachi et al. reported high-performance TADF-OLED devices in 2012, there have been many reports regarding the design and synthesis of new TADF luminogens, which have various molecular structures and are used for different applications. In this review, we summarize and discuss the latest progress concerning this rapidly developing research field, in which the majority of the reported TADF systems are discussed, along with their derived structure-property relationships, TADF mechanisms and applications. We hope that such a review provides a clear outlook of these novel functional materials for a broad range of scientists within different disciplinary areas and attracts more researchers to devote themselves to this interesting research field.