Efficient Room-temperature Phosphorescence Research Articles

Combining Functional Units to Design Organic Materials with Dynamic Room-Temperature Phosphorescence under Continuous Ultraviolet Irradiation.

Developing materials with dynamic room-temperature phosphorescence (RTP) properties is crucial for expanding the applications of organic light-emitting materials. In this study, we designed and synthesized two novel RTP molecules by combining functional units, incorporating the folded unit thianthrene into the classic luminescent cores thioxanthone or anthraquinone to construct TASO and TA2O. In this combination, the TA unit contributes to the enhancement of spin-orbit coupling (SOC), while the luminescent core governs the triplet energy level. After the strategic manipulation of SOC using the thianthrene unit, the target molecules exhibited a remarkable enhancement in RTP performance. This strategy led to the successful development of TASO and TA2O molecules with outstanding dynamic RTP properties when exposed to continuous ultraviolet irradiation, a result that can be ascribed to their efficient RTP, improved absorption ability, and oxygen-sensitive RTP properties. Leveraging the oxygen-mediated ultraviolet-radiation-induced RTP enhancement in TASO-doped polymer films, we developed a novel time-resolved detection technique for identifying phase separation in polymers with varying oxygen permeability. This research offers a promising approach for constructing materials with dynamic RTP properties.

Naphthyl substituted guest induce efficient room temperature phosphorescence by a triplet-triplet energy transfer mechanism

Room-temperature phosphorescent (RTP) materials have attracted more and more attention due to their long luminescence life and large Stokes displacement. Host-guest doping systems are highly regarded for their simplicity of preparation and the absence of complex synthesis processes. Strong RTP emission can be activated by the doping of a guest molecules, in particular by substituting the phenyl group in the host structure with a naphthalene group. In this study, derivatives of benzophenone were constructed as the host molecule, and used 2-Benzoylnaphthalene, a commercially available naphthyl-substituted analogue of benzophenone, as the guest molecule. The phosphorescent lifetime of the doped system can reach 335 ms and the phosphorescent quantum yield can reach 58 %, which is expected to be used in anti-counterfeiting encryption, biological imaging and other fields. This work provides a general and effective host-guest doping strategy for constructing various organic room temperature phosphorescent materials.

Scalable fabrication of red Room-Temperature phosphorescent materials through molecular doping strategy for versatile applications

Room-temperature phosphorescence (RTP) materials renowned for their long emission lifetime have garnered tremendous research interest not only for elucidating their underlying mechanisms but also for exploring their potential applications in anti-counterfeiting, encryption, and bioimaging. Nevertheless, the RTP color of most organic materials has been limited to blue, green, and yellow. In this study, a series of red RTP materials have been successfully fabricated at a large scale through a straightforward molecular doping strategy. Remarkably, the doped materials exhibited red RTP at 622 nm and 678 nm with an ultralong lifetime of 373 ms and an efficiency of 5.21 %, which was among the best performances reported for organic RTP materials. The systematic investigation unveiled that the efficient RTP emanated from the robust interactions between the emitter and matrix molecules as well as the formation of D/A exciplexes. Furthermore, the red RTP materials could be easily manufactured into diverse forms, including fine powders, aqueous inks, and nanoparticles. Their multifunctional applications in fingerprint recognition, encryption, and live bioimaging were demonstrated. With distinctive advantages such as red RTP, ultralong lifetime, scalable production, and cost-effectiveness, these RTP materials pave the way for the extensive utilization of organic RTP materials in various engineering sectors.

Multimode Stimuli-Responsive Room-Temperature Phosphorescence Achieved by Doping Butterfly-like Fluorogens into Crystalline Small-Molecular Hosts.

Materials with stimuli-responsive purely organic room-temperature phosphorescence (RTP) exempt from exquisite molecular design and complex preparation are highly desirable but still relatively rare. Moreover, most of them work in a single switching mode. Herein, we employ a versatile host-guest-doped strategy to facilely construct efficient RTP systems with multimode stimuli-responsiveness without ingenious molecular design. By conveniently doping butterfly-like guests, namely, N,N'-diphenyl-dihydrodibenzo[a,c]phenazines (DPACs), featured with vibration-induced emission into the small-molecular hosts via various methods, RTP systems with finely tunable photophysical properties are readily obtained. Through systematic mechanistic studies and with the aid of a series of control experiments, we unveil the critical role of the host crystallinity in achieving efficient RTP. By virtue of the inherent environmental sensitivity of both RTP and fluorescence of the DPACs, our systems exhibit multiple-stimuli-responsiveness with the luminescence not only switching between the fluorescence and phosphorescence but also continuously changing in the fluorescence color. Advanced dynamic anticounterfeiting and multilevel information encryption is thereby realized.

Achieving Efficient Room-Temperature Phosphorescence in the Host–Guest System through Covalent-Bond-Strengthened Hydrogen Bonding

Achieving Efficient Room-Temperature Phosphorescence in the Host–Guest System through Covalent-Bond-Strengthened Hydrogen Bonding

Achieving Efficient Dark Blue Room‐Temperature Phosphorescence with Ultra‐Wide Range Tunable‐Lifetime

AbstractTunable‐lifetime room‐temperature phosphorescence (RTP) materials have been widely studied due to their broad applications. However, only few reports have achieved wide‐range lifetime modulation. In this work, ultra‐wide range tunable‐lifetime efficient dark blue RTP materials were realized by doping methyl benzoate derivatives into polyvinyl alcohol (PVA) matrix. The phosphorescence lifetimes of the doped films can be increased from 32.8 ms to 1925.8 ms. Such wide range of phosphorescence lifetime modulation is extremely rare in current reports. Moreover, the phosphorescence emission of the methyl 4‐hydroxybenzoate‐doped film is located in the dark blue region and the phosphorescence quantum yield reaches as high as 15.4 %, which broadens their applications in organic optoelectronic information. Further studies demonstrated that the reason for the tunable lifetime was that the magnitude of the electron‐donating ability of the substituent group modulates the HOMO–LUMO and singlet‐triplet energy gap of methyl benzoate derivatives, as well as the ability to non‐covalent interactions with PVA. Moreover, the potential applications of luminescent displays and optical anti‐counterfeiting of these high‐performance dark blue RTP materials have been conducted.

Achieving Efficient Dark Blue Room-Temperature Phosphorescence with Ultra-Wide Range Tunable-Lifetime.

Tunable-lifetime room-temperature phosphorescence (RTP) materials have been widely studied due to their broad applications. However, only few reports have achieved wide-range lifetime modulation. In this work, ultra-wide range tunable-lifetime efficient dark blue RTP materials were realized by doping methyl benzoate derivatives into polyvinyl alcohol (PVA) matrix. The phosphorescence lifetimes of the doped films can be increased from 32.8 ms to 1925.8 ms. Such wide range of phosphorescence lifetime modulation is extremely rare in current reports. Moreover, the phosphorescence emission of the methyl 4-hydroxybenzoate-doped film is located in the dark blue region and the phosphorescence quantum yield reaches as high as 15.4 %, which broadens their applications in organic optoelectronic information. Further studies demonstrated that the reason for the tunable lifetime was that the magnitude of the electron-donating ability of the substituent group modulates the HOMO-LUMO and singlet-triplet energy gap of methyl benzoate derivatives, as well as the ability to non-covalent interactions with PVA. Moreover, the potential applications of luminescent displays and optical anti-counterfeiting of these high-performance dark blue RTP materials have been conducted.

Photophysical properties of DAPI in PVA films. Possibility of room temperature phosphorescence

We studied the spectral properties of 4′-6-diamidino-2-phenylindole (DAPI) in poly (vinyl alcohol) (PVA) films. Absorption and fluorescence spectra, emission and excitation spectra, quantum yield, and fluorescence lifetime have been characterized. An efficient room temperature phosphorescence (RTP) of DAPI has been observed with UV and blue light excitations. A few hundred millisecond phosphorescence lifetime enables a gated detection with sufficient background reduction. We found the phosphorescent Quantum Yield of DAPI in PVA Film to be 0.0009.

Achieving High-Temperature Phosphorescence by Organic Cocrystal Engineering.

Organic phosphors offer a promising alternative in optoelectronics, but their temperature-sensitive feature has restricted their applications in high-temperature scenarios, and the attainment of high-temperature phosphorescence (HTP) is still challenging. Herein, a series of organic cocrystal phosphors are constructed by supramolecular assembly with an ultralong emission lifetime of up to 2.16 s. Intriguingly, remarkable stabilization of triplet excitons can also be realized at elevated temperature, and green phosphorescence is still exhibited in solid state even up to 150 °C. From special molecular packing within the crystal lattice, it has been observed that the orientation of isolated water cluster and well-controlled molecular organization via multiple interactions can favor the structural rigidity of cocrystals more effectively to suppress the nonradiative transition, thus resulting in efficient room-temperature phosphorescence and unprecedented survival of HTP.

Enhancing Purely Organic Room Temperature Phosphorescence via Supramolecular Self-Assembly.

Long-lived and highly efficient room temperature phosphorescence (RTP) materials are in high demand for practical applications in lighting and display, security signboards, and anti-counterfeiting. Achieving RTP in aqueous solutions, near-infrared (NIR) phosphorescence emission, and NIR-excited RTP are crucial for applications in bio-imaging, but these goals pose significant challenges. Supramolecular self-assembly provides an effective strategy to address the above problems. This review focuses on the recent advances in the enhancement of RTP via supramolecular self-assembly, covering four key aspects: small molecular self-assembly, cocrystals, the self-assembly of macrocyclic hosts and guests, and multi-stage supramolecular self-assembly. This review not only highlights progress in these areas but also underscores the prominent challenges associated with developing supramolecular RTP materials. The resulting strategies for the development of high-performance supramolecular RTP materials are discussed, aiming to satisfy the practical applications of RTP materials in biomedical science.

Symmetry-Breaking Triplet Excited State Enhances Red Afterglow Enabling Ubiquitous Afterglow Readout.

Molecular vibrations are often factors that deactivate luminescence. However, if there are molecular motion elements that enhance luminescence, it may be possible to utilize molecular movement as a design guideline to enhance luminescence. Here, the authors report a large contribution of symmetry-breaking molecular motion that enhances red persistent room-temperature phosphorescence (RTP) in donor-π-donor conjugated chromophores. The deuterated form of the donor-π-donor chromophore exhibits efficient red persistent RTP with a yield of 21% and a lifetime of 1.6s. A dynamic calculation of the phosphorescence rate constant (kp) indicates that the symmetry-breaking movement has a crucial role in selectively facilitating kp without increasing nonradiative transition from the lowest triplet excited state. Molecules exhibiting efficient red persistent RTP enable long-wavelength excitation, indicating the suitability of observing afterglow readout in a bright indoor environment with a white-light-emitting diode flashlight, greatly expanding the range of anti-counterfeiting applications that use afterglow.

Organic Phosphorescent Hopper-Shaped Microstructures.

Hopper-shaped microcrystals, an unusual type of crystal with a large specific surface area, are promising for use in catalysis, drug delivery, and gas sensors. In contrast to well-studied inorganic hopper-shaped crystals, organic phosphorescent concave hopper-shaped microstructures are rarely reported. This study reports the synthesis of two types of organic stepped indented hopper-shaped microstructures with efficient room temperature phosphorescence (RTP) using a liquid phase self-assembly strategy. The formation mechanism is attributed to the interfacial instability induced by the concentration gradient and selective etching. Compared with flat microstructures, the stepped indented hopper-like RTP microstructures exhibit high sensitivity to oxygen. This work also demonstrates that packing the photochromic material into the concave hopper "vessel" effectively controls the switch of phosphorescence from energy transfer, expanding the potential applications of phosphorescent materials.

High-efficiency color-tunable ultralong room-temperature phosphorescence from organic-inorganic metal halides via synergistic inter/intramolecular interactions.

Materials exhibiting highly efficient, ultralong and multicolor-tunable room-temperature phosphorescence (RTP) are of practical importance for emerging applications. However, these are still very scarce and remain a formidable challenge. Herein, using precise structure design, several novel organic-inorganic metal-halide hybrids with efficient and ultralong RTP have been developed based on an identical organic cation (A). The original organic salt (ACl) exhibits red RTP properties with low phosphorescence efficiency. However, after embedding metals into the organic salt, the changed crystal structure endows the resultant metal-halide hybrids with excellent RTP properties. In particular, A2ZnCl4·H2O exhibits the highest RTP efficiency of up to 56.56% with a long lifetime of up to 159 ms. It is found that multiple inter/intramolecular interactions and the strong heavy-atom effect of the rigid metal-halide hybrids can suppress molecular motion and promote the ISC process, resulting in highly stable and localized triplet excitons followed by highly efficient RTP. More crucially, multicolor-tunable fluorescence and RTP achieved by tuning the metal and halogen endow these materials with wide application prospects in the fields of multilevel information encryption and dynamic optical data storage. The findings promote the development of phosphorescent metal-halide hybrids for potential high-tech applications.

Fast, Efficient, Narrowband Room-Temperature Phosphorescence from Metal-Free 1,2-Diketones: Rational Design and Mechanism

We report metal-free organic 1,2-diketones that exhibit fast and highly efficient room-temperature phosphorescence (RTP) with high colour purity under various conditions, including solutions. RTP quantum yields reached 38.2% in solution...

Recent progress in ion-regulated organic room-temperature phosphorescence.

Organic room-temperature phosphorescence (RTP) materials have attracted considerable attention for their extended afterglow at ambient conditions, eco-friendliness, and wide-ranging applications in bio-imaging, data storage, security inks, and emergency illumination. Significant advancements have been achieved in recent years in developing highly efficient RTP materials by manipulating the intermolecular interactions. In this perspective, we have summarized recent advances in ion-regulated organic RTP materials based on the roles and interactions of ions, including the ion-π interactions, electrostatic interactions, and coordinate interactions. Subsequently, the current challenges and prospects of utilizing ionic interactions for inducing and modulating the phosphorescent properties are presented. It is anticipated that this perspective will provide basic guidelines for fabricating novel ionic RTP materials and further extend their application potential.

Unique Visualization Growth Process of Long-Lived Room Temperature Phosphorescence in Polymer System.

Recently, embedding organic phosphors into the polyvinyl alcohol (PVA) matrix has emerged as a convenient strategy to obtain efficient long-lived room temperature phosphorescence (RTP) via forming strong intermolecular hydrogen bonds with organic phosphors to minimize nonradiative relaxations. Regrettably, it is discovered that PVA is unable to trigger RTP emission when a novel functional phosphor THBE containing six extended biphenyl formaldehyde arms is doped into PVA matrix. Surprisingly, the excellent long-lived RTP emission can be easily obtained by doping THBE into PVA analogs, poly(vinyl alcohol-co-ethylene) (PVA-co-PE). The unique visualization growth process (i.e., white streak generation) of long-lived RTP is observed by UV light-driven aggregation of functional molecules THBE in PVA-co-PE matrix. The phosphorescent intensity of the luminescent film is enhanced by 55 times, from 729 to 40,785 a.u., and its phosphorescence lifetime is increased by 38 times, from 37.08 to 1415.41ms. Due to the dynamically reversible RTP performance, as well as the permeability, flexibility, and wrinkle-free properties of the luminescent film, it can be utilized to create cutting-edge information storage devices.

Red Room-Temperature Phosphorescence Supramolecular Assemblies Based on Cucurbit[7]uril: Reversible Temperature Stimulation Response and Cell-Specific Silver Ion Imaging.

Solid-state materials with efficient room-temperature phosphorescence (RTP) emission have been widely used in materials science, and organic RTP-emitting systems with heavy-metal doping in aqueous solutions have attracted much attention in recent years. A novel supramolecular interaction was induced by host-guest assembly using cucurbit[7]uril (Q[7]) as the host and brominated naphthalimide phosphor as the guest. This interaction was further enhanced through synergistic chelation stimulated by analytical silver ion complexation. This approach facilitated the system's structural rigidity, intersystem crossing, and oxygen shielding. We achieved deep red phosphorescence emission in aqueous solution and ambient conditions along with quantitative determination of silver ions. The new complex exhibited good reversible thermoresponsive behavior and was successfully applied for the first time to target phosphorescence imaging of silver ions in the mitochondria of A549 cancer cells. These results are beneficial for constructing novel RTP systems with stimulus-responsive luminescence in aqueous solution, contributing to future research in bioimaging, detection, optical sensors, and thermometry materials.

Selenoxanthen-9-one-based emitters exhibiting efficient room temperature phosphorescence for electroluminescent and oxygen sensing applications

Two selenoxanthen-9-one-based emitters (Se-2DPA and Se-2TPA) were synthesized by introducing diphenylamine and triphenylamine as electron donors. The doped films of Se-2DPA and Se-2TPA exhibited bright fluorescence-phosphorescence dual emission and comparable photoluminescence quantum yields (ΦPL) of 31.4 % and 29.6 %, respectively. Unlike the Se-2DPA with phosphorescence lifetime of 1.1 ms, Se-2TPA shows significantly extended phosphorescence lifetime up to 17.7 ms. As revealed by computational and experimental investigations, Se-2DPA maintained more effective spin orbit coupling (SOC) between T1 and S0 states and its radiative rate constant of phosphorescence is 1 order of magnitude higher than that of Se-2TPA, which resulted in a relatively shorter phosphorescence lifetime. Consequently, solution-processed organic light-emitting diodes (OLEDs) based on Se-2DPA with shorter phosphorescence lifetime achieved a maximum external quantum efficiency of 8.8 %, which is much higher than the device based on Se-2TPA (only 0.8 %). In contrast, Se-2TPA showed higher sensitivity for oxygen sensing and the Stern-Volmer quenching constant (KSV) value reached 3.04 × 10−3 ppm owing to the longer phosphorescence lifetime, which is over 3-folds higher than that of Se-2DPA (8.88 × 10−4 ppm) under the same conditions.

Theoretical perspective for structural isomerism effect on photoelectric properties of organic room temperature phosphorescence molecules

Purely organic room temperature phosphorescence (RTP) materials have garnered extensive attentions in anti-counterfeiting and encryption, information display, biological imaging and organic light emitting diodes (OLEDs) due to the features of long lifetimes, low toxicity and good biocompatibility. Nevertheless, both the species and amounts of the efficient RTP molecules are far from meeting the requirements for practical applications, and the quantitative relationship between molecular structures and optoelectronic properties needs full elucidated. Herein, the photophysical properties and properties of three isomers (o-BA, m-BA and p-BA) are explored based on the first-principles calculations coupled with thermal vibration correlation function (TVCF) method and kinetic Monte Carlo simulations. The substituent effects on the molecular structures, intermolecular interactions, transition properties, Huang-Rhys factors and reorganization energies, excited state dynamics as well as transfer integrals and charge carrier mobilities are investigated in detail to clarify the structure-property relationships. Results show that o-BA achieves fast radiative rate on account of impressive transition dipole moment and oscillator strength, but equally large non-radiative decay rate leads to low RTP efficiency. Promisingly, the highest holes mobility is determined for o-BA due to the largest transfer integrals of holes originating from the strong intermolecular interactions. In addition, compared with o-BA and p-BA, m-BA could achieve fast intersystem crossing (ISC) rate with large spin orbit coupling constant and low non-radiative decay rate with small geometric structure changes. Relatively balanced holes and electrons mobilities of m-BA have been demonstrated, which contributes to the recombination of excitons and the improvement of luminescence efficiency. For p-BA, the strong intermolecular hydrogen bonding restricts the free rotation of single bonds and promotes the molecular coplanarity, which contributes to efficient emission. Furthermore, the charge mobility is calculated and the temperature dependence is investigated, the hopping mechanisms for studied isomers are illustrated. This work reveals the relationship among molecular structures, crystal packing modes, photophysical properties and charge transport properties of isomers, and provides an insight for molecular design and property prediction.

Single-Molecular White Emission of Organic Thianthrene-Based Luminophores Exhibiting Efficient Fluorescence and Room Temperature Phosphorescence Induced by Halogen Atoms

Single-Molecular White Emission of Organic Thianthrene-Based Luminophores Exhibiting Efficient Fluorescence and Room Temperature Phosphorescence Induced by Halogen Atoms