A Heavy-atom-free Molecular Motif Based on Symmetric Bird-like Structured Tetraphenylenes with Room-Temperature Phosphorescence (RTP) Afterglow over 8 s

In recent years, pure organic room-temperature phosphorescence (RTP) with highly efficient and long-persistent afterglow has drawn substantial awareness. Commonly, spin-orbit coupling can be improved by introducing heavy atoms into pure-organic molecules. However, this strategy will simultaneously increase the radiative and non-radiative transition rate, further resulting in dramatic decreases in the excited state lifetime and afterglow duration. Here in this work, a highly symmetric bird-like structure tetraphenylene (TeP), and its three symmetrical halogenated derivatives (TeP−F, TeP−Cl and TeP−Br) are synthesized, while their RTP properties and mechanisms are systematically investigated by both theoretical and experimental approaches. As the results, the rigid, highly twisted conformation of TeP restricts the non-radiative processes of RTP and gives rise to the enhancement of electron-exchange, which can contribute to the RTP radiation process. Despite the faint RTP of the bromine and chlorine-substituted ones (TeP−Br, TeP−Cl), the fluoro-substituted TeP−F exhibited a long phosphorescent lifetime up to 890 ms, corresponding to an extremely long RTP afterglow over 8 s, which could be incorporated into the best series of non-heavy-atom RTP materials reported in previous literature.     

Long-Persistent Circularly Polarized Luminescence from a Host-Guest System Regulated by the Multiple Roles of a Gold(I)-Carbene Motif

The promotion of intersystem crossing (ISC) is critical for achieving a high-efficiency long-persistent luminescence (LPL) from organic materials. However, the use of a transition-metal complex for LPL materials has not been explored because it can also shorten the emission lifetime by accelerating the phosphorescence decay. Here, we report a new class of LPL materials by doping a monovalent Au-carbene complex into a boron-embedded molecular host. The donor-acceptor systems exhibit photoluminescence with both high efficiencies (>57 %) and long lifetimes (ca. 40 ms) at room temperature. It is revealed that the Au atom promotes the population of low-lying triplet excited states of the host aggregate (T₁*) which can be converted into the charge-transfer (CT) state, thereby resulting in afterglow luminescence. Moreover, the use of a chirality unit on the guest molecule results in the LPL being circularly polarized. This work illustrates that transition-metal complexes can be used for developing organic afterglow systems by exquisite control over the excited state mechanism.     

Color-Tunable Dual-Mode Organic Afterglow for White-Light Emission and Information Encryption Based on Carbazole Doping

Dual-mode emission materials, combining phosphorescence and delayed fluorescence, offer promising opportunities for white-light afterglow. However, the delayed fluorescence lifetime is usually significantly shorter than that of phosphorescence, limiting the duration of white-light emission. In this study, a carbazole-based host–guest system that can be activated by both ultraviolet (UV) and visible light is reported to achieve balanced phosphorescence and delayed fluorescence, resulting in a long-lived white-light afterglow. Our study demonstrated the critical role of a charge transfer state in the afterglow mechanism, where the charge separation and recombination process directly determined the lifetime of afterglow. Simultaneously, an efficient reversed intersystem crossing process was obtained between the singlet and triplet charge transfer states, which facilitating the delayed fluorescence properties of host–guest system. As a result, delayed fluorescence lifetime was successfully prolonged to approach that of phosphorescence. This work presents a delayed fluorescence lifetime improvement strategy via doping method to realize durable white-light afterglow.     

Long Afterglow Room‐Temperature Phosphorescence from Nanopebbles: A Urea Pyrolysis Product

Materials having long afterglow are highly sought after for various applications such as light‐emitting diodes, security signs and bioimaging. Herein, we report a simple, low‐cost synthesis of a purely organic room‐temperature phosphorescent nanomaterial with a pebble‐like structure by heating urea, a biocompatible and easily available precursor, at 200 °C with a high phosphorescence lifetime of 1.0365 s and a visible afterglow for up to 10 s. This urea derived phosphorescent nanocomposite (UPNC) can be mixed with commercially available acrylic paint base and common gum, which can be readily used as a phosphorescent pigment.     

Fluorine-induced aggregate-interlocking for color-tunable organic afterglow with a simultaneously improved efficiency and lifetime

Designing organic afterglow materials with a high efficiency and long lifetime is highly attractive but challenging because of the inherent competition between the luminescence efficiency and lifetime. Here, we propose a simple yet efficient strategy, namely fluorine-induced aggregate-interlocking (FIAI), to realize both an enhanced efficiency and elongated lifetime of afterglow materials by stimulating the synergistic effects of the introduced fluorine atoms to efficiently promote intersystem crossing (ISC) and intermolecular non-covalent interactions for facilitating both the generation of triplet excitons and suppression of non-radiative decays. Thus, the fluorine-incorporated afterglow molecules exhibit greatly enhanced ISC with a rate constant up to 5.84 × 10⁷ s⁻¹ and suppressed non-radiative decay down to 0.89 s⁻¹, resulting in efficient organic afterglow with a simultaneously improved efficiency up to 10.5% and a lifetime of 1.09 s. Moreover, accompanied by the efficient phosphorescence emission especially at cryogenic temperature, color-tunable afterglow was also observed at different temperatures. Therefore, tri-mode multiplexing encryption devices by combining lifetime, temperature and color, and visual temperature sensing were successfully established. The FIAI strategy by addressing fundamental issues of afterglow emission paves the way to develop high-performance organic afterglow materials, opening up a broad prospect of aggregated and excited state tuning of organic solids for emission lifetime-resolved applications.

Through the fluorine-induced aggregate-interlocking (FIAI) strategy, the designed afterglow materials showed both improved quantum yields and prolonged lifetimes by breaking through the intrinsic bottlenecks of organic afterglow.     

反尖晶石结构的Mg2SnO4系长余辉材料的研究进展及应用

Mg2SnO4具有典型的反尖晶石结构,由于存在大量缺陷,非常适合作为长余辉材料的基质材料,而且其成本低,结构稳定光学性能优异,应用前景非常广泛。通过在反尖晶石结构的Mg2SnO4材料中掺杂不同离子可以制备出不同性质的长余辉材料。本文主要介绍了Mg2SnO4系长余辉材料的常用的制备工艺方法和发光机理,从离子掺杂的角度分析其性能,并对反尖晶石结构的Mg2SnO4系长余辉材料在防伪、信息存储、成像等方面的应用现状进行了综述和展望。     

A Universal Strategy for Activating the Multicolor Room‐Temperature Afterglow of Carbon Dots in a Boric Acid Matrix

Carbon dots (CDs) have attracted attention in metal‐free afterglow materials, but most CDs were heteroatom‐containing and the afterglow emissions are still limited to the short‐wavelength region. A universal approach to activate the room‐temperature phosphorescence (RTP) of both heteroatom‐free and heteroatom‐containing CDs was developed by one‐step heat treatment of CDs and boric acid (BA). The introduction of an electron‐withdrawing boron atom in composites can greatly reduce the energy gap between the singlet and triplet state; the formed glassy state can effectively protect the excited triplet states of CDs from nonradiative deactivation. A universal host for embedding CDs to achieve long‐lifetime and multi‐color (blue, green, green‐yellow and orange) RTP via a low cost, quick and facile process was developed. Based on their distinctive RTP performances, the applications of these CD‐based RTP materials in information encryption and decryption are also proposed and demonstrated.     

Dye Sensitization Offers a Brighter Afterglow Nanoparticle Future for in vivo Recharged Luminescent Imaging

While concerns about improving recharged afterglow intensity in vivo still motivate further exploration, afterglow nanoparticles (AGNP) offer unique optical merit for autofluorescence-free biological imaging. Apart from efforts enhancing the afterglow emission properties of AGNP, improving afterglow excitation response to visible or near infrared light is important but has lacked success. Dye sensitization has been used to improve the optical response of photovoltaic nanomaterials and to enhance upconversion luminescence efficiency. This concept has recently been expanded and applied to AGNPs. As a new multifunctional nanoprobe, such dye-sensitized AGNP takes advantage of both high spatial resolution fluorescence imaging and sensitive afterglow imaging. This Concept introduces the background, the concept, mechanism, and related imaging application, as well as reviewing existing challenges and proposing future developmental directions for the dye-sensitized AGNPs.     

Efficient metal-free organic room temperature phosphors

An innovative transformation of organic luminescent materials in recent years has realised the exciting research area of ultralong room-temperature phosphorescence. Here the credit for the advancements goes to the rational design of new organic phosphors. The continuous effort in the area has yielded wide varieties of metal-free organic systems capable of extending the lifetime to several seconds under ambient conditions with high quantum yield and attractive afterglow properties. The various strategies adopted in the past decade to manipulate the fate of triplet excitons suggest a bright future for this class of materials. To analyze the underlying processes in detail, we have chosen high performing organic triplet emitters that utilized the best possible ways to achieve a lifetime above one second along with impressive quantum yield and afterglow properties. Such a case study describing different classes of metal-free organic phosphors and strategies adopted for the efficient management of triplet excitons will stimulate the development of better candidates for futuristic applications. This Perspective discusses the phosphorescence features of single- and multi-component crystalline assemblies, host–guest assemblies, polymers, and polymer-based systems under various classes of molecules. The various applications of the organic phosphors, along with future perspectives, are also highlighted.

A summary of the extremely efficient organic phosphors that utilized the best possible ways to manipulate the fate of triplet excitons for achieving a long lifetime along with impressive quantum yield and afterglow properties is provided.     

Ultra-long Near-infrared Repeatable Photochemical Afterglow Mediated by Reversible Storage of Singlet Oxygen for Information Encryption

Photochemical afterglow systems have drawn considerable attention in recent years due to their regulable photophysical properties and charming application potential. However, conventional photochemical afterglow suffered from its unrepeatability due to the consumption of energy cache units as afterglow photons are emitted. Here we report a novel strategy to realize repeatable photochemical afterglow (RPA) through the reversible storage of ¹O₂ by 2-pyridones. Near-infrared afterglow with a lifetime over 10 s is achieved, and its initial intensity shows no significant reduction over 50 excitation cycles. A detailed mechanism study was conducted and confirmed the RPA is realized through the singlet oxygen-sensitized fluorescence emission. Furthermore, the generality of this strategy is demonstrated and tunable afterglow lifetimes and colors are achieved by rational design. The developed RPA is further applied for attacker-misleading information encryption, presenting a repeatable-readout.     

Round‐the‐Clock Photocatalytic Hydrogen Production with High Efficiency by a Long‐Afterglow Material

Long afterglow materials can store and release light energy after illumination. A brick‐like, micrometer‐sized Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ long‐afterglow material is used for hydrogen production by the photocatalytic reforming of methanol under round‐the‐clock conditions for the first time, achieving a solar‐to‐hydrogen (STH) conversion efficiency of 5.18 %. This material is one of the most efficient photocatalysts and provides the possibility of practical use on a large scale. Its remarkable photocatalytic activity is attributed to its unique carrier migration path and large number of lattice defects. These findings expand the application scope of long afterglow materials and provide a new strategy to design efficient photocatalysts by constructing trap levels that can prolong carrier lifetimes.     

Ultra-Small Air-Stable Triplet-Triplet Annihilation Upconversion Nanoparticles for Anti-Stokes Time-Resolved Imaging

Image contrast is often limited by background autofluorescence in steady-state bioimaging microscopy. Upconversion bioimaging can overcome this by shifting the emission lifetime and wavelength beyond the autofluorescence window. Here we demonstrate the first example of triplet-triplet annihilation upconversion (TTA-UC) based lifetime imaging microscopy. A new class of ultra-small nanoparticle (NP) probes based on TTA-UC chromophores encapsulated in an organic–inorganic host has been synthesised. The NPs exhibit bright UC emission (400–500 nm) in aerated aqueous media with a UC lifetime of ≈1 μs, excellent colloidal stability and little cytotoxicity. Proof-of-concept demonstration of TTA-UC lifetime imaging using these NPs shows that the long-lived anti-Stokes emission is easily discriminable from typical autofluorescence. Moreover, fluctuations in the UC lifetime can be used to map local oxygen diffusion across the subcellular structure. Our TTA-UC NPs are highly promising stains for lifetime imaging microscopy, affording excellent image contrast and potential for oxygen mapping that is ripe for further exploitation.     

Visualization of microscale particle focusing in diluted and whole blood using particle trajectory analysis

Inertial microfluidics has demonstrated the potential to provide a rich range of capabilities to manipulate biological fluids and particles to address various challenges in biomedical science and clinical medicine. Various microchannel geometries have been used to study the inertial focusing behavior of particles suspended in simple buffer solutions or in highly diluted blood. One aspect of inertial focusing that has not been studied is how particles suspended in whole or minimally diluted blood respond to inertial forces in microchannels. The utility of imaging techniques (i.e., high-speed bright-field imaging and long exposure fluorescence (streak) imaging) primarily used to observe particle focusing in microchannels is limited in complex fluids such as whole blood due to interference from the large numbers of red blood cells (RBCs). In this study, we used particle trajectory analysis (PTA) to observe the inertial focusing behavior of polystyrene beads, white blood cells, and PC-3 prostate cancer cells in physiological saline and blood. Identification of in-focus (fluorescently labeled) particles was achieved at mean particle velocities of up to 1.85 m s(-1). Quantitative measurements of in-focus particles were used to construct intensity maps of particle frequency in the channel cross-section and scatter plots of particle centroid coordinates vs. particle diameter. PC-3 cells spiked into whole blood (HCT = 45%) demonstrated a novel focusing mode not observed in physiological saline or diluted blood. PTA can be used as an experimental frame of reference for understanding the physical basis of inertial lift forces in whole blood and discover inertial focusing modes that can be used to enable particle separation in whole blood.     

Temperature‐Correlated Afterglow of a Semiconducting Polymer Nanococktail for Imaging‐Guided Photothermal Therapy

Nanoparticles for photothermal therapy: Real‐time temperature monitoring is critical to reduce the nonspecific damage during photothermal therapy (PTT); however, PTT agents that can emit temperature‐related signals are rare and limited to few inorganic nanoparticles. We herein synthesize a semiconducting polymer nanococktail (SPN_CT) that can not only convert photo‐energy to heat but also emit temperature‐correlated luminescence after cessation of light excitation. Such an afterglow luminescence of the SPN_CT detects tumors more sensitively than fluorescence as a result of the elimination of tissue autofluorescence, while its temperature‐dependent nature allows tumor temperature to be optically monitored under near‐infrared (NIR) laser irradiation. Thus, SPN_CT represents the first organic optical nanosystem that enables optical‐imaging guided PTT without real‐time light excitation.     

Evaluation of groundwater recharge sources based on environmental tracers in an arid alluvial fan,NW China

Although there are many new scintillators being developed recently, CsI: Tl is still a very efficient one among them. However it suffers from afterglow which limits application in high-speed x-ray imaging. In order to find out the mechanism of afterglow and the method to suppress afterglow in CsI: Tl, the theoretical model of perfect CsI, CsI: Tl and CsI: Tl, Eu are built by the software Material Studio. The total and partial density of states of these three models is calculated within the framework of generalized gradient approximation and ultra-soft pseudo-potential. The results indicate that the generation of afterglow in CsI: Tl is due to the impurity energy bands introduced by Tl. Moreover, co-doping CsI: Tl with Eu will introduce deeper impurity energy bands which can effectively scavenge the electrons trapped by the shallow impurity energy bands introduced by Tl, thus suppressing the afterglow in CsI: Tl.

     

Non-linear fluorescence lifetime imaging of biological tissues

In recent years fluorescence microscopy has become a widely used tool for tissue imaging and spectroscopy. Optical techniques, based on both linear and non-linear excitation, have been broadly applied to imaging and characterization of biological tissues. Among fluorescence techniques used in tissue imaging applications, in recent years two and three-photon excited fluorescence have gained increased importance because of their high-resolution deep tissue imaging capability inside optically turbid samples. The main limitation of steady-state fluorescence imaging techniques consists in providing only morphological information; functional information is not detectable without technical improvements. A spectroscopic approach, based on lifetime measurement of tissue fluorescence, can provide functional information about tissue conditions, including its environment, red-ox state, and pH, and hence physiological characterization of the tissue under investigation. Measurement of the fluorescence lifetime is a very important issue for characterizing a biological tissue. Deviation of this property from a control value can be taken as an indicator of disorder and/or malignancy in diseased tissues. Even if much work on this topic has still to be done, including the interpretation of fluorescence lifetime data, we believe that this methodology will gain increasing importance in the field of biophotonics. In this paper, we review methodologies, potentials and results obtained by using fluorescence lifetime imaging microscopy for the investigation of biological tissues.     

Manipulation of Organic Afterglow by Thermodynamic and Kinetic Control

The fabrication of room-temperature organic phosphorescence and afterglow materials, as well as the transformation of their photophysical properties, has emerged as an important topic in the research field of luminescent materials. Here, we report the establishment of energy landscapes in dopant-matrix organic afterglow systems where the aggregation states of luminescent dopants can be controlled by doping concentrations in the matrices and the methods of preparing the materials. Through manipulation by thermodynamic and kinetic control, dopant-matrix afterglow materials with different aggregation states and diverse afterglow properties can be obtained. The conversion from metastable aggregation state to thermodynamic stable aggregation state of the dopant-matrix afterglow materials to leads to the emergence of intriguing afterglow transformation behavior triggered by thermal and solvent annealing. The thermodynamically unfavorable reversible afterglow transformation process can also be achieved by coupling the dopant-matrix afterglow system to mechanical forces.     

Purely Organic Fluorescence Afterglow: Visible-Light-Excitation,Inherent Mechanism,Tunable Color,and Practical Applications with Very Low Cost

Purely organic materials with visible light excitable fluorescence afterglow are promising for applications. Herein, fluorescence afterglow with various intensity and duration was observed on fluorescent dyes once being dispersed in polymer matrix, thanks to the slow reverse intersystem crossing rate (k_RISC) and long delayed fluorescence lifetime (τ_DF) derived from the coplanar and rigid chemical structure of the dyes. To verify the mechanism, different polymers were used to tune singlet-triplet splitting energy based on solvent effect. And commercial acriflavine (Acf) film showed blue shifted fluorescence compared to purified one, with slower k_RISC (≈10⁰ s⁻¹) and longer τ_DF (0.6 s). Via energy transfer from Acf to rhodamine B, the afterglow color was further regulated, with the largest fluorescence quantum yield of 42.4 %. It was demonstrated that the materials worked on color tunable light sources, and low-cost ($2 for 50 000 labels) anti-counterfeit labels recognized by white light.     

长余辉发光材料在陶瓷行业的应用研究

长余辉发光材料和陶／搪瓷材料的结合始于80年代,当时采用的是传统的硫化物体系长余辉发光材料。20世纪90年代,随着多种新型长余辉材料的发现,使性能更佳的长余辉陶／搪瓷制品的开发成为可能。本文介绍新型铝酸盐体系、硅酸盐体系及新型红色长余辉材料应用于低温陶／搪瓷釉料（800－900℃）、中温陶瓷釉料（980－1100℃）,及将低温陶／搪瓷釉料、中温陶瓷釉料应用于陶／搪瓷制品的研究,以及将各种新型长余辉材料应用于花纸、玻璃行业中。这种长余辉陶／瓷制品性能稳定、发光强度达到发光粉的80％,发光时间可达12h以上;而且应用工艺简单,可直接用传统的陶／搪瓷制品工艺进行生产。     

掺铥硫氧化钇的特殊余辉性质

迄今为止,稀土长余辉磷光体已见文献或专利公开报道的激活离子主要有适于紫外光激发的三价铈离子(Ce³⁺)和三价镨离子(Pr³⁺)、适于可见光激发的铕离子(Eu³⁺和Eu²⁺)及钐离子(Sm³⁺,Sm²⁺),尚未涉及到铥离子Tm³⁺或Tm²⁺.我们在Tm³⁺离子激活的硫氧化钇体系Y₂O₂S:Tm³⁺中发现了长余辉荧光特性.特别是在该磷光体中还发现了一种非常特殊的余辉现象.