Organic Phosphorescence Research Articles

Employing racemization strategies to simultaneously enhance the quantum yield, lifetime, and water stability of room-temperature phosphorescent materials.

Room temperature phosphorescence (RTP) materials are increasingly recognized for their superior luminescent properties, which are pivotal in applications such as anti-counterfeiting, information storage, and optoelectronics. Despite this, the sensitivity of most RTP systems to humidity presents a significant challenge in achieving durable RTP performance in aqueous environments. This study proposes a strategy to enhance organic room-temperature phosphorescence through racemization. By incorporating external racemates of various chiral phosphors-NDBD-Ph, NDBD-Ph-Ph, NDBD-CH3, and NDBD-O-CH3-into a polyacrylonitrile (PAN) matrix, we significantly enhance the RTP properties (quantum yield, lifetime, and afterglow-time) of the resultant films. This enhancement can be attributed to the increased density of racemic molecules in the matrix and the increased spin-orbit coupling (SOC), facilitating the development of a long-lasting polymer RTP system in water. Notably, the racemic rac-NDBD-Ph@PAN film exhibits a persistent bright turquoise afterglow, even after immersion in water for a month. Furthermore, for the first time, we achieved an enhanced green to cyan RTP response to pH variations under both acidic and alkaline conditions (pH = 2-12), with the maximum phosphorescence emission intensity increasing up to threefold. The remarkable water stability, reversible response characteristics, and enhanced phosphorescence properties of this system offer promising potential for dynamic information encryption in aqueous environments.

Utilizing weakly donor-acceptor ternary π-conjugated architecture to achieve single-component white luminescence and stimulus-responsive room-temperature phosphorescence.

Purely organic room-temperature phosphorescence (RTP) has garnered substantial attention for its delayed emission, environmental sensitivity, and potential diverse applications. However, the quest for high-performance RTP materials has always been a challenge. In this study, we introduce novel weakly donor-acceptor (D-A) ternary π-conjugated architecture to construct an efficient RTP system. The strategy utilizes synergistic effects of the analogous El-Sayed rule, halogen-free heavy-atom effect, reduction of the singlet-triplet energy gap, and manipulation of flexible molecular conformation. A remarkable enhancement in the phosphorescence-to-fluorescence ratio was achieved, elevating from 0.4 in carbazole to 35.2 in DBTDBTCZ. Furthermore, the RTP system demonstrates single-component white luminescence, yielding warm and cool white colors. Intriguingly, we unveil the novel position-dependent heavy-atom effects, discerningly promoting intersystem crossing or phosphorescence decay. Benefiting from efficient RTP, multifunctional applications of real-time humidity monitoring, oxygen sensing, anti-counterfeiting labeling, and white lighting are demonstrated.

Multi-colour room-temperature phosphorescence from fused-ring compounds for dynamic anti-counterfeiting applications.

We present a facile strategy to achieve purely organic multi-colour room-temperature phosphorescence (RTP) films by doping typical fused-ring compounds into a poly(vinyl alcohol) matrix. Such RTP films demonstrate inherent RTP emission ranging from green to red with a long lifetime and high quantum yield (QY) (lifetime: ∼0.56 ms, QY: ∼35.4%). We further exploit such high-performance RTP films for dynamic information encryption.

Phosphorescent acyclic cucurbituril solid supramolecular multicolour delayed fluorescence behaviour.

Organic photoluminescent macrocyclic hosts have been widely advanced in many fields. Phosphorescent hosts with the ability to bind organic guests have rarely been reported. Herein, acyclic cucurbituril modified with four carboxylic acids (ACB-COOH) is mined to present uncommon purely organic room-temperature phosphorescence (RTP) at 510 nm with a lifetime of 1.86 μs. Its RTP properties are significantly promoted with an extended lifetime up to 2.12 s and considerable quantum yield of 6.29% after assembly with a polyvinyl alcohol (PVA) matrix. By virtue of the intrinsic self-crimping configuration of ACB-COOH, organic guests, including fluorescence dyes (Rhodamine B (RhB) and Pyronin Y (PyY)) and a drug molecule (morphine (Mor)), could be fully encapsulated by ACB-COOH to attain energy transfer involving phosphorescent acyclic cucurbituril. Ultimately, as-prepared systems are successfully exploited to establish multicolor afterglow materials and visible sensing of morphine. As an expansion of phosphorescent acyclic cucurbituril, the host afterglow color can be readily regulated by attaching different aromatic sidewalls. This study develops the fabrication strategies and application scope of a supramolecular phosphorescent host and opens up a new direction for the manufacture of intelligent long-lived luminescent materials.

Modulating the crystal packing to achieve efficient ultralong organic phosphorescence by simple methylation engineering

Simple methylation engineering strategy used to adjust the packing and UOP behavior is demonstrated. The intrinsic relationship between structure and UOP properties are investigated by combining the experimental and theoretical results.

Triplet-triplet energy transfer between host and guest induced strong phosphorescence in the organic doped system

Recently, purely organic room-temperature phosphorescence (RTP) from guest-host-doped systems has grown exponentially due to their high modulation flexibility. Benzophenone has been found as a preferred host matrix thanks to its low melting point, minimal biological toxicity, remarkable stability, and cost-effectiveness. However, the precise role of benzophenone remains elusive and has been debated within the scientific community concerning mechanistic elucidations. Here, five indole derivatives were designed and synthesized as guest molecules while retaining benzophenone as the host to construct doped materials exhibiting outstanding RTP properties. Our experimental findings unequivocally establish that the host benzophenone initially absorbs excitation energy, subsequently intersystem crossing into triplet exciton, facilitating the exciton transfer to guest molecule through the triplet energy transfer and culminating in guest RTP emission. Mechanistic investigation corroborates the superiority of benzophenone in possessing a large spin-orbit coupling constant and quantitatively triplet energy transfer. Collectively, this work provides compelling evidence deciphering energy transfer between host and guest entities for the manifestation of phosphorescence performance in benzophenone-hosted doped materials.

Fused-Ring Pyrrole-Based Near-Infrared Emissive Organic RTP Material for Persistent Afterglow Bioimaging.

Organic near-infrared room temperature phosphorescence (RTP) materials offer remarkable advantages in bioimaging due to their characteristic time scales and background noise elimination. However, developing near-infrared RTP materials for deep tissue imaging still faces challenges since the small band gap may increase the non-radiative decay, resulting in weak emission and short phosphorescence lifetime. In this study, fused-ring pyrrole-based structures were employed as the guest molecules for the construction of long wavelength emissive RTP materials. Compared to the decrease of the singlet energy level, the triplet energy level showed a more effectively decrease with the increase of the conjugation of the substituent groups. Moreover, the sufficient conjugation of fused ring structures in the guest molecule suppresses the non-radiative decay of triplet excitons. Therefore, a near-infrared RTP material (764 nm) was achieved for deep penetration bioimaging. Tumor cell membrane is used to coat RTP nanoparticles (NPs) to avoid decreasing the RTP performance compared to traditional coating by amphiphilic surfactants. RTP NPs with tumor-targeting properties show favorable phosphorescent properties, superior stability, and excellent biocompatibility. These NPs are applied for time-resolved luminescence imaging to eliminate background interference with excellent tissue penetration. This study provides a practical solution to prepare long-wavelength and long-lifetime organic RTP materials and their applications in bioimaging.

Precisely Coordination‐Modulated Ultralong Organic Phosphorescence Enables Biomimetic Fluorescence‐Afterglow Dual‐Modal Information Encryption

AbstractInformation leakage and counterfeiting are serious worldwide issues that tremendously impact legitimate businesses and human life. Inspired by the Noctiluca scintillans, a new fluorescence‐afterglow dual‐modal information encryption enabled by precisely coordination‐modulated ultralong organic phosphorescence (UOP) is presented. Strikingly, the optical properties including fluorescence, lifetime and intensity of UOP can be precisely modulated on‐demand through energy transfer by lanthanide (LnIII) coordination, which enables information camouflage by similar LnIII luminescence to provide misleading information along with data decryption in the form of mutual afterglow. Moreover, the important data can be encrypted in a spatial‐time‐resolved way by programmatically coding information with afterglow gradients, yielding greatly improved security for verifying the authenticity. This study provides a new avenue to precisely modulate the optical properties of UOP materials and broadens the scope of optical materials for innovative information encryption and anticounterfeiting applications.

Circularly Polarized Organic Ultralong Room-Temperature Phosphorescence with A High Dissymmetry Factor in Chiral Helical Superstructures.

Long-lived room-temperature phosphorescence (RTP) of organic materials holds a significant potential for optical information. Circularly polarized organic ultralong room-temperature phosphorescence (CP-OURTP) with extremely high dissymmetry factor (glum ) values is even highly demanded and considerably challenging. Here, an effective strategy is introduced to realize CP-OURTP with an emission decay time of 735ms and a glum value up to 1.49, which exceeds two orders of magnitude larger than previous records, through a system composed of RTP polymers and chiral helical superstructures. The system exhibits excellent stability under multiple cycles of photoirradiation and thermal treatment, and is further employed for information encryption based on optical multiplexing. The results are anticipated to lay the foundation for the development of CP-OURTP materials in advanced photonic applications.

Photo-Responsive Dynamic Organic Room-Temperature Phosphorescence Materials Based on a Functional Unit Combination Strategy.

A rational molecular design strategy facilitates the development of a purely organic room-temperature phosphorescence (RTP) material system with precisely regulated luminescence properties, which surely promotes its functional integration and intelligent application. Here, a functional unit combination strategy is proposed to design novel RTP molecules combining a folding unit with diverse luminescent cores. The different luminescent cores are mainly responsible for tunable RTP properties, while the folding unit contributes to the spin-orbit coupling (SOC) enhancement, which makes the RTP material design as workable as the building block principle. By this strategy, a series of color/lifetime-tunable RTP materials is achieved with unique photo-responsive RTP enhancement when subjected to UV irradiation, which expands their application scenarios in reusable privacy tags, advanced "4D" encryption, and phase separation analysis of blended polymers. This work suggests a simple and effective strategy to design purely organic RTP materials with tunable color and lifetime, and also provides new application options for photo-responsive dynamic RTP materials.

Dual-Stimulus-Driven Dynamically Controllable [3]Rotaxane with Tunable Organic Room-Temperature Phosphorescence.

A dual-stimulus-driven stiff-stilbene-based dynamic [3]rotaxane has been facilely developed using the threading-stoppering strategy and exhibits reversible shuttling motions and bidirectional rotations upon encountering acid-base and distinct light stimulations, respectively. Herein, the two dibenzo-24-crown-8 macrocycles can undergo reversible switching motion between two different stations along the axle suffered from acid-base stimulation, and simultaneously, the two rotaxanes can also perform cis-trans rotations upon irradiation with distinct light. In other words, the constructed rotaxanes can conduct two modes of regular motions without interference. Interestingly, reciprocating switching motion of the rings along the axle enabled the rotaxanes to exhibit controllable and reversible photoisomerization speed, conversion yield, and quantum yield. Crucially, these rotaxanes also manifest adjustable solid-state organic room-temperature phosphorescence (RTP) and photoluminescence stimulated by dual factors (acid-base and diverse light), which are further applied in information encryption and anticounterfeiting. The presented study provides an instructive way for precisely boosting photoisomerization performances and the fabrication of dual-stimuli-induced molecular machines with functions of two-mode mechanical motions and controllable pure organic RTP switches.

Achieving color-tunable persistent afterglow from ultralong polyacrylamide-based room-temperature phosphorescence materials through phosphorescence Förster resonance energy transfer

Polymer-based pure organic room-temperature phosphorescence (RTP) materials have received widespread attention due to their great application prospects in many fields. However, the reports about polymer-based multicolor RTP materials were still rare. Herein, a series of monochromatic PAM-based RTP materials are constructed by facilely doping boric acid derivatives into polyacrylamide (PAM) matrices. Due to the strong intermolecular hydrogen-bonding interaction, 4-carboxyphenylboronic acid (CPBA) doped system PAM/CPBA achieves an ultralong RTP lifetime of 753 ms with a naked-eye visible blue afterglow up to 12 s. Significantly, PAM/CPBA as energy donor and the commercial fluorescent dye fluorescein (FL) or rhodamine B (RhB) as energy acceptor are used to fabricated ternary doping systems to achieve multicolor afterglow emission through phosphorescence Förster resonance energy transfer (FRET). The afterglow colors of PAM/CPBA/FL and PAM/CPBA/RhB can be easily adjusted from blue to yellow or purple by changing the doping content of FL or RhB. Inspiringly, a nearly white afterglow emission from the quaternary doping system PAM/CPBA/RhB/FL is achieved by varying the amount of FL content. Furthermore, the prepared PAM-based binary and ternary doping RTP materials can be applied in the field of information encryption.

Phosphorescence resonance energy transfer from purely organic supramolecular assembly.

Phosphorescence energy transfer systems have been applied in encryption, biomedical imaging and chemical sensing. These systems exhibit ultra-large Stokes shifts, high quantum yields and are colour-tuneable with long-wavelength afterglow fluorescence (particularly in the near-infrared) under ambient conditions. This review discusses triplet-to-singlet PRET or triplet-to-singlet-to-singlet cascaded PRET systems based on macrocyclic or assembly-confined purely organic phosphorescence introducing the critical toles of supramolecular noncovalent interactions in the process. These interactions promote intersystem crossing, restricting the motion of phosphors, minimizing non-radiative decay and organizing donor-acceptor pairs in close proximity. We discuss the applications of these systems and focus on the challenges ahead in facilitating their further development.

Regulating isolated-molecular and aggregated state phosphorescence for multi-color afterglow by photo-activation.

Ultralong organic phosphorescence (UOP) materials have attracted considerable attention in recent years. Herein, a new type of flexible films was fabricated by doping amphipathic pyrene tetra sulfonic acid sodium salts into amorphous poly(vinyl alcohol) matrix, which enabled the realization of color-tunable UOP spanning from orange-red to green after excitation light switched off. Interestingly, we demonstrated precise control of the proportion of isolated-molecular and aggregated state phosphorescence for colorful afterglow using photo-activation. A 2.19-fold increase in the dynamic phosphorescence lifetime of isolated molecules was observedfrom 752.94 to 1650.46 ms following an 8-minute irradiation under ambient conditions. This flexible and processable film exhibited versatile applications in multi-color afterglow displays, ultraviolet detection, multilevel information encryption, etc. Our study not only provides a strategy for the rational regulation of UOP colors but also expands the application potential of color-tunable UOP materials. This article is protected by copyright. All rights reserved.

Polymeric ultralong organic phosphorescence with excellent humidity and temperature resistance via hydrophobic effect

AbstractPolymeric ultralong organic phosphorescence (UOP) with persistent emission is of great importance in practical applications. However, achieving good water‐resistance for long‐term environmental stability is a formidable challenge. In this contribution, through tailoring the alkyl‐chain length of the hardeners and emitters, polymeric UOPs with varying crosslinking density and hydrophobic effect were obtained. Notably, all the polymers show no obvious decrease in UOP emission after high temperature‐humidity test (85°C/85% relative humidity for 7 days). Detailed investigations demonstrate that the rigid covalent crosslinking networks suppress the quenching of triplet excitons while the hydrophobic microenvironment affords good water/moisture‐resistance ability. Moreover, the polymers with superior processability are successfully applied as optical coatings, prepreg, and afterglow displays. With this work, we provide a new strategy to promote the long‐term stability of polymeric UOP materials in high‐temperature‐humidity conditions.

Axially chiral materials exhibiting blue-emissive ultralong organic phosphorescence and intense circularly polarized luminescence

Axially chiral materials exhibiting blue-emissive ultralong organic phosphorescence and intense circularly polarized luminescence

Chaperone Mimetic Strategy for Achieving Organic Room-Temperature Phosphorescence based on Confined Supramolecular Assembly.

The development of organic materials that deliver room-temperature phosphorescence (RTP) is highly interesting for potential applications such as anticounterfeiting, optoelectronic devices, and bioimaging. Herein, a molecular chaperone strategy for controlling isolated chromophores to achieve high-performance RTP is demonstrated. Systematic experiments coupled with theoretical evidence reveal that the host plays a similar role as a molecular chaperone that anchors the chromophores for limited nonradiative decay and directs the proper conformation of guests for enhanced intersystem crossing through noncovalent interactions. For deduction of structure-property relationships, various structure-related descriptors that correlate with the RTP performance are identified, thus offering the possibility to quantitatively design and predict the phosphorescent behaviors of these systems. Furthermore, application in thermal printing is well realized for these RTP materials. The present work discloses an effective strategy for efficient construction of organic RTP materials, delivering a modular model which is expected to help expand the diversity of desirable RTP systems.

Achieving Stable and Switchable Ultralong Room-Temperature Phosphorescence from Polymer-Based Luminescent Materials with Three-Dimensional Covalent Networks for Light-Manipulated Anticounterfeiting.

Developing polymer-based organic afterglow materials with switchable ultralong organic phosphorescence (UOP) that are insensitive to moisture remains challenging. Herein, two organic luminogens, BBCC and BBCS, were synthesized by attaching 7H-benzo[c]carbazole (BBC) to benzophenone and diphenyl sulfone. These two emitters were employed as guest molecules and doped into epoxy polymers (EPs), which were constructed by in situ polymerization to achieve polymer materials BBCC-EP and BBCS-EP. It was found that BBCC-EP and BBCS-EP films exhibited significant photoactivated UOP properties. After light irradiation, they could produce a conspicuous organic afterglow with phosphorescence quantum yields and lifetimes up to 5.35% and 1.91 s, respectively. Meanwhile, BBCS-EP also presented photochromic characteristics. Upon thermal annealing, the UOP could be turned off, and the polymer films recovered to their pristine state, showing switchable organic afterglow. In addition, BBCC-EP and BBCS-EP displayed excellent water resistance and still produced obvious UOP after soaking in water for 4 weeks. Inspired by the unique photoactivated UOP and photochromic properties, BBCC and BBCS in the mixtures of diglycidyl ether of bisphenol A (DGEBA) and 1,3-propanediamine were employed as security inks for light-controlled multilevel anticounterfeiting. This work may provide helpful guidance for developing photostimuli-responsive polymer-based organic afterglow materials, especially those with stable UOP under ambient conditions.

Time-Dependent Colorful Circularly Polarized Organic Ultralong Room Temperature Phosphorescence from a Single-Component Chiral Molecule.

Colorful circularly polarized organic ultralong room temperature phosphorescence (CP-OURTP) materials have attracted much attention due to their superior optoelectronic properties for various applications. However, the development of colorful CP-OURTP materials in a single-component molecular system is currently facing great challenges. Herein, a feasible strategy is proposed to develop colorful CP-OURTP material from a single-component chiral molecule by introducing a chiral unit into the phosphorescence chromophore. A dual CP-OURTP band originated from inherent triplet excitons emission showing a lifetime of 946.44ms and triplet-triplet annihilation induced delayed emission with a short lifetime of 209.91ms as well as maximum asymmetry factors of ≈10-3 are realized. Owing to the changed OURTP intensity ratios between inherent CP-OURTP and delayed emission at different delayed times, time-dependent colorful CP-OURTP turned from yellow to green is obtained. This study provides a potential platform to prepare circularly polarized material systems showing colorful luminescent properties.

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

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 centrosymmetric 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 of 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.