Organic Phosphorescent Materials Research Articles

Efficient intersystem crossing and tunable ultralong organic room-temperature phosphorescence via doping polyvinylpyrrolidone with polyaromatic hydrocarbons

Polymer-based pure organic room-temperature phosphorescent materials have tremendous advantages in applications owing to their low cost, vast resources, and easy processability. However, designing polymer-based room-temperature phosphorescent materials with large Stokes shifts as key requirements in biocompatibility and environmental-friendly performance is still challenging. By generating charge transfer states as the gangplank from singlet excited states to triplet states in doped organic molecules, we find a host molecule (pyrrolidone) that affords charge transfer with doped guest molecules, and excellent polymer-based organic room-temperature phosphorescent materials can be easily fabricated when polymerizing the host molecule. By adding polyaromatic hydrocarbon molecules as electron-donor in polyvinylpyrrolidone, efficient intersystem crossing and tunable phosphorescent from green to near-infrared can be achieved, with maximum phosphorescence wavelength and lifetime up to 757 nm and 3850 ms, respectively. These doped polyvinylpyrrolidone materials have good photoactivation properties, recyclability, advanced data encryption, and anti-counterfeiting. This reported design strategy paves the way for the design of polyvinylpyrrolidone-based room-temperature phosphorescent materials.

Urea-formaldehyde resin room temperature phosphorescent material with ultra-long afterglow and adjustable phosphorescence performance

Organic room-temperature phosphorescence materials have attracted extensive attention, but their development is limited by the stability and processibility. Herein, based on the on-line derivatization strategy, we report the urea-formaldehyde room-temperature phosphorescence materials which are constructed by polycondensation of aromatic diamines with urea and formaldehyde. Excitingly, urea-formaldehyde room-temperature phosphorescence materials achieve phosphor lifetime up to 3326 ms. There may be two ways to enhance phosphorescence performance, one is that the polycondensation of aromatic diamine with urea and formaldehyde promotes spin-orbit coupling, and another is that the imidazole derivatives derived from the condensation of aromatic o-diamine with formaldehyde maintains low levels of energy level difference and spin-orbit coupling, thus achieving ultra-long afterglow. Surprisingly, urea-formaldehyde room-temperature phosphorescence materials exhibit tunable phosphorescence emission in electrostatic field. Accordingly, 1,4-phenylenediamine, urea, and formaldehyde are copolymerized and self-assembled into phosphorescence microspheres with different electrostatic potential strengths. By mixing 1 wt% 1,4-phenylenediamine polycondensation microspheres with 1,4-phenylenediamine free microspheres, phosphor lifetime of the composite could be regulated from 27 ms to 123 ms. Moreover, vulcanization process enables precise shaping of urea-formaldehyde room-temperature phosphorescence materials. This work not only demonstrates that urea-formaldehyde room-temperature phosphorescence materials are promising candidates for organic phosphors, but also exhibits the phenomenon of electrostatically regulated phosphorescence.

An Organophosphorescence Probe with Ultralong Lifetime and Intrinsic Tissue Selectivity for Specific Tumor Imaging and Guided Tumor Surgery.

Organic phosphorescent materials are excellent candidates for use in tumor imaging. However, a systematic comparison of the effects of the intensity, lifetime, and wavelength of phosphorescent emissions on bioimaging performance has not yet been undertaken. This study addresses these gaps and reveals that longer lifetimes effectively increase the signal intensity, whereas longer wavelengths enhance the penetration depth. Conversely, a strong emission intensity with a short lifetime does not necessarily yield robust imaging signals. Building upon these findings, an organo-phosphorescent material with a lifetime of 0.94 s was designed for tumor imaging. Remarkably, the phosphorescent signals of various organic nanoparticles are nearly extinguished in blood-rich organs because of the quenching effect of iron ions. Moreover, for the first time, we demonstrated that iron ions universally quench the phosphorescence of organic room-temperature phosphorescent materials, which is an inherent property of such substances. Leveraging this property, both the normal liver and hepatitis tissues exhibit negligible phosphorescent signals, whereas liver tumors display intense phosphorescence. Therefore, phosphorescent materials, unlike chemiluminescent or fluorescent materials, can exploit this unique inherent property to selectively distinguish liver tumor tissues from normal tissues without additional modifications or treatments.

An Organophosphorescence Probe with Ultralong Lifetime and Intrinsic Tissue Selectivity for Specific Tumor Imaging and Guided Tumor Surgery

Organic phosphorescent materials are excellent candidates for use in tumor imaging. However, a systematic comparison of the effects of the intensity, lifetime, and wavelength of phosphorescent emissions on bioimaging performance has not yet been undertaken. This study addresses these gaps and reveals that longer lifetimes effectively increase the signal intensity, whereas longer wavelengths enhance the penetration depth. Conversely, a strong emission intensity with a short lifetime does not necessarily yield robust imaging signals. Building upon these findings, an organo‐phosphorescent material with a lifetime of 0.94 s was designed for tumor imaging. Remarkably, the phosphorescent signals of various organic nanoparticles are nearly extinguished in blood‐rich organs because of the quenching effect of iron ions. Moreover, for the first time, we demonstrated that iron ions universally quench the phosphorescence of organic room‐temperature phosphorescent materials, which is an inherent property of such substances. Leveraging this property, both the normal liver and hepatitis tissues exhibit negligible phosphorescent signals, whereas liver tumors display intense phosphorescence. Therefore, phosphorescent materials, unlike chemiluminescent or fluorescent materials, can exploit this unique inherent property to selectively distinguish liver tumor tissues from normal tissues without additional modifications or treatments.

Highly stable ultralong organic phosphorescence from a 3D organic supramolecule constructed by halogen bonding and π–π interactions

Ultralong organic phosphorescence (UOP) materials have offered new exciting possibilities in the fields of photoelectric device, scintillators, anti-counterfeiting and bioprobe. However, pure organic phosphorescent materials inevitably suffer from rapid nonradiative transitions under oxygen, humidity, and high temperature, rending their phosphorescence is significantly quenched. Herein, a three-dimensional (3D) organic supramolecule (named SFIz) featuring UOP property was constructed successfully. Impressively, benefiting from the unique halogen bonding and π–π interactions, dual phosphorescent emission route of high energy state T1 (Br···O interaction predominates) and low energy state T1* (π–π interaction predominates) was simultaneously realized. Furthermore, owing to the robust supramolecular structural characteristic, SFIz shows highly stable UOP property with remarkably thermal, force stimulus and water-resistant stabilities that can be applied directly in extreme environments such as high temperatures 453 K (180 °C), high pressure and humidity. This work not only provides a much needed solution for achieving highly stable UOP materials and promoting their applications in extreme environments, but also gives in-depth understanding of both UOP and dual phosphorescent emission mechanisms in a non-metallic organic molecule.

Responsive organic room-temperature phosphorescence materials for spatial-time-resolved anti-counterfeiting

Stimulus-responsive room-temperature phosphorescence (RTP) materials have gained significant attention for their important optoelectronic application prospects. However, the fabrication strategy and underlying mechanism of stimulus-responsive RTP materials remain less explored. Herein, we present a reliable strategy for achieving pH-responsive RTP materials by integrating poly(vinyl alcohol) (PVA) with carboxylic acid or amino group functionalized terpyridine (Tpy) derivatives. The resulting Tpy derivatives-based RTP materials displayed reversible changes in emission color, intensity, and lifetime of both prompt and delayed emission. Notably, the RTP emission undergoes a significant diminish upon exposure to acid due to the protonation of Tpy units. Taking advantage of the decent RTP emission and pH-responsiveness of these RTP films, a spatial-time-resolved anti-counterfeiting application is demonstrated as a proof-of-concept for largely enhancing the security level. This study not only provides new prospects for developing smart RTP materials but also promotes the advancement of optical anti-counterfeiting applications.

Manipulation of Photo‐Active Ultralong Organic Phosphorescence in Host‐Guest System

AbstractThe photo‐active ultralong organic phosphorescence (UOP) materials can only emit UOP gradually under consistent UV irradiation, which is primarily attributed to internal quenching of triplet oxygen, yet manipulating the rate of the photo‐activating process is seldom reported. In addition, amorphous small‐molecule doping UOP material is rarely reported either. In this study, a series of host and guest materials are synthesized and doped into amorphous UOP doping systems. These doping systems demonstrated a tunable photo‐activating rate (4–6 seconds to reach a saturated state), and the amorphous structure realized the sensitive detection of oxygen. The results affirm that triplet oxygen plays a pivotal role in determining whether UOP can be emitted, and importantly, it is established that a crystalline structure in small‐molecular doping systems is not a necessary condition. Furthermore, polymer‐based UOP materials, manufactured through co‐doping with both host and guest, exhibited tunable photo‐activating rates (4–16 s) and lifetimes (226.38–462.78 ms). To expand the application, the UV‐curing resin‐based UOP materials are prepared via 3D‐printing technology. This innovative work introduces a new approach for applying UOP materials in the field of amorphous doping system, providing a guiding strategy for widespread applications in oxygen detecting, time‐resolved information display and dynamic multi‐dimensional anti‐counterfeiting.

Biobased and biodegradable films exhibiting circularly polarized room temperature phosphorescence

There is interest in developing sustainable materials displaying circularly polarized room-temperature phosphorescence, which have been scarcely reported. Here, we introduce biobased thin films exhibiting circularly polarized luminescence with simultaneous room-temperature phosphorescence. For this purpose, phosphorescence-active lignosulfonate biomolecules are co-assembled with cellulose nanocrystals in a chiral construct. The lignosulfonate is shown to capture the chirality generated by cellulose nanocrystals within the films, emitting circularly polarized phosphorescence with a 0.21 dissymmetry factor and 103 ms phosphorescence lifetime. By contrast with most organic phosphorescence materials, this chiral-phosphorescent system possesses phosphorescence stability, with no significant recession under extreme chemical environments. Meanwhile, the luminescent films resist water and humid environments but are fully biodegradable (16 days) in soil conditions. The introduced bio-based, environmentally-friendly circularly polarized phosphorescence system is expected to open many opportunities, as demonstrated here for information processing and anti-counterfeiting.

Twofold rigidity activates ultralong organic high-temperature phosphorescence

A strategy is pioneered for achieving high-temperature phosphorescence using planar rigid molecules as guests and rigid polymers as host matrix. The planar rigid configuration can resist the thermal vibration of the guest at high temperatures, and the rigidity of the matrix further enhances the high-temperature resistance of the guest. The doped materials exhibit an afterglow of 40 s at 293 K, 20 s at 373 K, 6 s at 413 K, and a 1 s afterglow at 433 K. The experimental results indicate that as the rotational ability of the groups connected to the guests gradually increases, the high-temperature phosphorescence performance of the doped materials gradually decreases. In addition, utilizing the property of doped materials that can emit phosphorescence at high temperatures and in high smoke, the attempt is made to use organic phosphorescence materials to identify rescue workers and trapped personnel in fires.

Constructing [2.2]Paracyclophane‐Based Ultrasensitive Optical Fluorescent‐Phosphorescent Thermometer with Cucurbit[8]uril Supramolecular Assembly

AbstractThe pursuit of developing novel approaches to fully organic and efficient phosphorescent materials is in high demand. The optical activity of such functional, organic phosphorescent/fluorescent materials may exhibit great temperature dependence, allowing their application as advanced, highly sensitive molecular thermometers. In this study, a rational strategy involving host–guest complexation and polymerization of [2.2]paracyclophane (PCP) based molecules with cucurbit[8]uril (CB8) to suppress the molecular motion and promote temperature‐dependent phosphorescence is presented. The rigid cavity of CB8 provides an ideal microenvironment to host PCP molecules 1 and 2, significantly enhancing the photophysical performance after complexation. Co‐polymerizing phosphors 1 and 2 with acrylamide is an efficient method for improving phosphorescence. Incorporating CB8 into the resulting P‐1 and P‐2 polymers enhances phosphorescence performance. Importantly, the obtained materials exhibit a big structure‐dependent spectral shift and change of phosphorescence lifetimes with temperature, allowing novel, phosphorescence‐based, and purely organic optical thermometers to be developed. The practical applications of PCP‐based luminescent materials in temperature sensing via a multi‐parameter approach are showcased, i.e., using fluorescence spectral shift and changes in bandwidth, as well as phosphorescence lifetimes, exhibiting thermal sensitivity of ≈17.7 cm−1 °C−1, 47.8 cm−1 °C, and 5.2% °C−1, respectively.

Polymorphism-Dependent Organic Room Temperature Phosphorescent Scintillation for X-Ray Imaging.

Organic phosphorescent scintillating materials have shown great potential for applications in radiography and radiation detection due to their efficient utilization of excitons. However, revealing the relationship between molecule stacking and the phosphorescent radioluminescence of scintillators is still challenging. This study reports on two phenothiazine derivatives with polymorphism-dependent phosphorescence radioluminescence. The experiments reveal that molecule stacking significantly affects the non-radiation decay of the triplet excitons of scintillators, which further determines the phosphorescence scintillation performance under X-ray irradiation. These phosphorescent scintillators exhibit high radio stability and have a low detection limit of 278 nGys-1. Additionally, the potential application of these scintillators in X-ray radiography, based on their X-ray excited radioluminescence properties, is demonstrated. These findings provide a guideline for obtaining high-performance phosphorescent scintillating materials by shedding light on the effect of crystal packing on the radioluminescence of organic molecules.

Significant room-temperature phosphorescence enhancement induced by matrix complexes

Incorporating phosphors into polymer matrix is a relatively mature method to develop organic room-temperature phosphorescent (RTP) materials but still needs to be further explored because of limited investigations about the effect of different matrix on the RTP properties of the same guest molecule. Colorful RTP (from blue to red, with τafterglow up to 1736 ms) in carboxymethyl chitosan (CC) systems was achieved in this work. To improve the RTP performance, quaternary chitosan (QC) was introduced to build a binary matrix system, which extended the lifetime by 200 ms and increased the phosphorescence quantum yield to 3.51 times. Systematic characterizations and theoretical calculations indicated that the RTP materials obtained from binary matrix had higher ion group density and stronger dipole–dipole interactions, which could narrow the singlet–triplet energy gap and promote the triplet excitons generation. Compared to single matrix, binary matrix could also provide more crosslinked networks to better stabilize triplet excitons, thus synergistically enhancing the RTP. Finally, based on the good biocompatibility and antibacterial properties of chitosan and phosphorescent emission, the films were expected to be used for monitoring the integrity of the package and multiple antibacterial coating films.

Conformational Effect of Catechol-Terephthalonitrile Emitters Leading to Ambient Violet Phosphorescence.

Organic ambient violet phosphorescent (AVP) materials are of great interest due to their involvement of high energy and longer-lived triplet excitons. Here, we show three fused ring functionalized donor-acceptor-donor (D-A-D/D-A-D') emitters (BPT1-BPT3), in which two catechol-based donors (3,4-dihydroxybenzophenone, catechol, or 3,5-ditert-butylcatechol) are covalently fused to the terephthalonitrile acceptor via four O-C single bonds. Spectroscopic analysis revealed that all the molecules show AVP (∼390-394 nm, τAVP = 73-101 μs) with phosphorescence quantum yields (ϕP) of 1.8-27.4% due to low singlet-triplet gaps (0.036-0.046 eV) and conformational effects. BPT3 with bulky tert-butyl groups increases AVP (ϕP = 27.4%). Quantum chemistry calculations reveal flat (F1) and twisted (F2) conformers (ground state) with a low energy difference (∼4-5 kcal/mol) for all molecules; the F1 conformer is responsible for efficient AVP, while weak blue thermally activated delayed fluorescence with longer-lived delayed components is realized from the F2 conformer. This approach may provide important clues for the design of high-energy organic phosphorescent materials.

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.

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.

Thia[n]helicenes with long persistent phosphorescence.

Helicenes with persistent luminescence have received relatively little attention, despite their demonstrated highly efficient intersystem crossing (ISC) from the excited singlet to the triplet state. Herein, we designed a series of ortho-fused aromatics by combining dithieno[2,3-b:3',2'-d]thiophene (DTT) with annulated benzene fragments, denoted as TB[n]H (n = 3-8), to achieve persistent luminescence. Wherein, thia[n]helicenes (n = 5-8) exhibited intense phosphorescence with millisecond-range lifetimes (τp) at 77 K. Particularly interesting was the observation that the odd-numbered ring helicenes displayed longer τp values than their neighboring even-numbered counterparts. Notably, TB[7]H showcased the longest τp of 628 ms. This phenomenon can be attributed to the more favorable ISC channels and stronger spin-orbital coupling (SOC) of old-numbered helicenes than even-numbered ones. Furthermore, both conformers of TB[7]H exhibited significant circularly polarized phosphorescent (CPP) responses, with luminescence dissymmetry factors (glum) of 0.015 and -0.014. These discoveries suggest that thiahelicenes may be a specific class of organic phosphorescent and CPP 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.

π-π Interaction-Induced Organic Long-wavelength Room-Temperature Phosphorescence for In Vivo Atherosclerotic Plaque Imaging.

Room-temperature phosphorescent (RTP) materials have great potential for in vivo imaging because they can circumvent the autofluorescence of biological tissues. In this study, a class of organic-doped long-wavelength (≈600 nm) RTP materials with benzo[c][1,2,5] thiadiazole as a guest was constructed. Both host and guest molecules have simple structures and can be directly purchased commercially at a low cost. Owing to the long phosphorescence wavelength of the doping system, it exhibited good tissue penetration (10 mm). Notably, these RTP nanoparticles were successfully used to image atherosclerotic plaques, with a signal-to-background ratio (SBR) of 44.52. This study provides a new approach for constructing inexpensive red organic phosphorescent materials and a new method for imaging cardiovascular diseases using these materials.

π–π Interaction‐Induced Organic Long‐wavelength Room‐Temperature Phosphorescence for In Vivo Atherosclerotic Plaque Imaging

AbstractRoom‐temperature phosphorescent (RTP) materials have great potential for in vivo imaging because they can circumvent the autofluorescence of biological tissues. In this study, a class of organic‐doped long‐wavelength (≈600 nm) RTP materials with benzo[c][1,2,5] thiadiazole as a guest was constructed. Both host and guest molecules have simple structures and can be directly purchased commercially at a low cost. Owing to the long phosphorescence wavelength of the doping system, it exhibited good tissue penetration (10 mm). Notably, these RTP nanoparticles were successfully used to image atherosclerotic plaques, with a signal‐to‐background ratio (SBR) of 44.52. This study provides a new approach for constructing inexpensive red organic phosphorescent materials and a new method for imaging cardiovascular diseases using these materials.

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.