Platinum complexes with aggregation-induced emission.

Transition metal-containing materials with aggregation-induced emission (AIE) have brought new opportunities for the development of biological probes, optoelectronic materials, stimuli-responsive materials, sensors, and detectors. Coordination compounds containing the platinum metal have emerged as a promising option for constructing effective AIE platinum complexes. In this review, we classified AIE platinum complexes based on the number of ligands. We focused on the development and performance of AIE platinum complexes with different numbers of ligands and discussed the impact of platinum ion coordination and ligand structure variation on the optoelectronic properties. Furthermore, this review analyzes and summarizes the influence of molecular geometries, stacking models, and aggregation environments on the optoelectronic performance of these complexes. We provided a comprehensive overview of the AIE mechanisms exhibited by various AIE platinum complexes. Based on the unique properties of AIE platinum complexes with different numbers of ligands, we systematically summarized their applications in electronics, biological fields, etc. Finally, we illustrated the challenges and opportunities for future research on AIE platinum complexes, aiming at giving a comprehensive summary and outlook on the latest developments of functional AIE platinum complexes and also encouraging more researchers to contribute to this promising field.

Introducing Spiro-locks into the Nitrogen/Carbonyl System towards Efficient Narrowband Deep-blue Multi-resonance TADF Emitters.

The current availability of multi-resonance thermally activated delayed fluorescence (MR-TADF) materials with excellent color purity and high device efficiency in the deep-blue region is appealing. To address this issue in the emerged nitrogen/carbonyl MR-TADF system, we propose a spiro-lock strategy. By incorporating spiro functionalization into a concise molecular skeleton, a series of emitters (SFQ, SOQ, SSQ, and SSeQ) can enhance molecular rigidity, blue-shift the emission peak, narrow the emission band, increase the photoluminescence quantum yield by over 92 %, and suppress intermolecular interactions in the film state. The referent CZQ without spiro structure has a more planar skeleton, and its bluer emission in the solution state redshifts over 40 nm with serious spectrum broadening and a low PLQY in the film state. As a result, SSQ achieves an external quantum efficiency of 25.5 % with a peak at 456 nm and a small full width at half maximum of 31 nm in a simple unsensitized device, significantly outperforming CZQ. This work discloses the importance of spiro-junction in modulating deep-blue MR-TADF emitters.

Design and Synthesis of Red Through-Space Charge Transfer Thermally Activated Delayed Fluorescence Emitters with Donor/Acceptor/Donor Stacking.

Red through-space charge transfer thermally activated delayed fluorescence (TSCT TADF) materials named SAF36DCPP and SAF27DCPP with sandwiched structures were synthesized. Single crystals indicated that the intramolecular C-H···π interactions play a vital role in rigidifying the sandwiched structure, which results in a fluorescence yield of 63% for SAF36DCPP compared to 40% for SAF27DCPP. Organic light-emitting diodes with SAF36DCPP as the emitter realized a maximum external quantum efficiency of 16.12%.

Highly Efficient Sky-Blue π-Stacked Thermally Activated Delayed Fluorescence Emitter with Multi-Stimulus Response Properties.

Organic materials with multi-stimulus response (MSR) properties have demonstrated many potential and practical applications. Herein, a π-stacked thermally activated delayed fluorescence (TADF) material with multi-stimulus response (MSR) properties, named SDMAC, was designed and synthesized using distorted 9,9-dimethyl-10-phenyl-9,10-dihydroacridine as a donor. SDMAC possesses a rigid π-stacked configuration with intramolecular through-space interactions and exhibits aggregation-induced emission enhancement (AIEE), solvatochromic, piezochromic, and circularly polarized luminescence (CPL) under different external stimuli. The rigid molecular structure and efficient TADF properties of SDMAC can be used in displays and lighting. Using SDMAC as an emitter, the maximum external quantum efficiency (EQE) of the fabricated organic light-emitting diodes (OLEDs) is as high as 28.4 %, which make them the most efficient CP-TADF OLEDs based on the through-space charge transfer strategy. The CP organic light-emitting diodes (CP-OLEDs) exhibit circularly polarized electroluminescence (CPEL) signals.

Pure Hydrocarbon Materials as Highly Efficient Host for White Phosphorescent Organic Light-Emitting Diodes: A New Molecular Design Approach.

To date, all efficient host materials reported for phosphorescent OLEDs (PhOLEDs) are constructed with heteroatoms, which have a crucial role in the device performance. However, it has been shown in recent years that the heteroatoms not only increase the design complexity but can also be involved in the instability of the PhOLED, which is nowadays the most important obstacle to overcome. Herein, we design pure aromatic hydrocarbon materials (PHC) as very efficient hosts in high-performance white and blue PhOLEDs. With EQE of 27.7 %, the PHC-based white PhOLEDs display similar efficiency as the best reported with heteroatom-based hosts. Incorporated as a host in a blue PhOLED, which are still the weakest links of the technology, a very high EQE of 25.6 % is reached, surpassing, for the first time, the barrier of 25 % for a PHC and FIrpic blue emitter. This performance shows that the PHC strategy represents an effective alternative for the future development of the OLED industry.

Atrial fibrillation burden and the risk of stroke: A systematic review and dose-response meta-analysis.

BACKGROUND: The increased stroke risk associated with atrial fibrillation (AF) burden exceeding 5 min is a matter of debate. In addition, the potential linear or nonlinear relationship between AF burden and stroke risk has been largely unexplored. AIM: To determine the association between AF burden > 5 min and the increased risk of stroke and explore the potential dose-response relationship between these two factors. METHODS: Sixteen studies from six databases with 53141 subjects (mean age 65 years) were included. Fifteen studies were observational studies, and one was a randomized controlled trial study. The potential nonlinear dose-response association was characterized using a restricted cubic splines regression model. AF burden for each 1 h and 2 h was associated with an increased risk of stroke. Trial sequential analysis with a random-effect model was used to evaluate the robustness of the evidence from the included 16 studies. RESULTS: AF burden > 5 min was associated with an increased risk of clinical AF [adjusted risk ratio (RR) = 4.18, 95% confidence interval (CI): 2.26-7.74]. However, no association was found with an increased risk of all-cause mortality (adjusted RR = 1.55, 95%CI: 0.87-2.75). Patients with AF burden > 5 min had an increased risk of stroke (adjusted RR = 2.49, 95%CI: 1.79-3.47). Moreover, a dose-response analysis showed that the increased stroke risk was paralleled by an increase in AF burden at a rate of 2.0% per hour (P nonlinear = 0.656, RR = 1.02, 95%CI: 1.01-1.03). Trial sequential analysis provided robust evidence of the association between AF burden > 5 min and an increased risk of stroke. CONCLUSION: AF burden was a significant risk factor for clinical AF and future stroke. A significant linear association was documented between increased AF burden and risk of future stroke.

Research Progress of Intramolecular π-Stacked Small Molecules for Device Applications.

Organic semiconductors can be designed and constructed in π-stacked structures instead of the conventional π-conjugated structures. Through-space interaction (TSI) occurs in π-stacked optoelectronic materials. Thus, unlike electronic coupling along the conjugated chain, the functional groups can stack closely to facilitate spatial electron communication. Using π-stacked motifs, chemists and materials scientists can find new ways for constructing materials with aggregation-induced emission (AIE), thermally activated delayed fluorescence (TADF), circularly polarized luminescence (CPL), and room-temperature phosphorescence (RTP), as well as enhanced molecular conductance. Organic optoelectronic devices based on π-stacked molecules have exhibited very promising performance, with some of them exceeding π-conjugated analogues. Recently, reports on various organic π-stacked structures have grown rapidly, prompting this review. Representative molecular scaffolds and newly developed π-stacked systems could stimulate more attention on through-space charge transfer the well-known through-bond charge transfer. Finally, the opportunities and challenges for utilizing and improving particular materials are discussed. The previous achievements and upcoming prospects may provide new insights into the theory, materials, and devices in the field of organic semiconductors.

A narrowband blue circularly polarized thermally activated delayed fluorescence emitter with a hetero-helicene structure.

A narrowband blue CP-TADF emitter with a rigid hetero-helicene structure (QAO-PhCz) was synthesized and characterized. QAO-PhCz exhibits good electroluminescence performance (EQE = 14.0%) and narrow FWHM. The enantiomers of QAO-PhCz display CPL and CPEL properties with |glum| and |gEL|values of up to 1.1 × 10-3 and 1.5 × 10-3, respectively.

Cascaded Excited-State Intramolecular Proton Transfer Towards Near-Infrared Organic Lasers Beyond 850†nm.

Near-infrared (NIR) organic solid-state lasers play an essential role in applications ranging from laser communication to infrared night vision, but progress in this area is restricted by the lack of effective excited-state gain processes. Herein, we originally proposed and demonstrated the cascaded occurrence of excited-state intramolecular proton transfer for constructing the completely new energy-level systems. Cascading by the first ultrafast proton transfer of <430 fs and the subsequent irreversible second proton transfer of ca. 1.6 ps, the stepwise proton transfer process favors the true six-level photophysical cycle, which supports efficient population inversion and thus NIR single-mode lasing at 854 nm. This work realizes longest wavelength beyond 850 nm of organic single-crystal lasing to date and originally exploits the cascaded excited-state molecular proton transfer energy-level systems for organic solid-state lasers.

Fully Bridged Triphenylamine Derivatives as Color-Tunable Thermally Activated Delayed Fluorescence Emitters.

Three emissive bridged-triphenylamine derivatives are designed and synthesized by incorporating carbon (DQAO), oxygen (OQAO), and sulfur (SQAO) atoms with two carbonyl groups. The fully bridged geometry and unique frontier molecular orbital distribution reveal its potential as narrowband thermally activated delayed fluorescence emitters. DQAO-, OQAO-, and SQAO-based organic light-emitting diodes exhibit the maximum external quantum efficiency (EQEmax) of 15.2%, 20.3%, and 17.8% for blue, green, and yellow, respectively.

Multi-Layer π-Stacked Molecules as Efficient Thermally Activated Delayed Fluorescence Emitters.

Multi-layer π-stacked emitters based on spatially confined donor/acceptor/donor (D/A/D) patterns have been developed to achieve high-efficiency thermally activated delayed fluorescence (TADF). In this case, dual donor moieties and a single acceptor moiety are introduced to form two three-dimensional (3D) emitters, DM-BD1 and DM-BD2, which rely on spatial charge transfer (CT). Owing to the enforced face-to-face D/A/D pattern, effective CT interactions are realized, which lead to high photoluminescence quantum yields (PLQYs) of 94.2 % and 92.8 % for the two molecules, respectively. The resulting emitters exhibit small singlet-triplet energy splitting (ΔEST ) and fast reverse intersystem crossing (RISC) processes. Maximum external quantum efficiencies (EQEs) of 28.0 % and 26.6 % were realized for devices based on DM-BD1 and DM-BD2, respectively, which are higher than those of their D/A-type analogues.

Circularly Polarized Thermally Activated Delayed Fluorescence Emitters in Through-Space Charge Transfer on Asymmetric Spiro Skeletons.

This work describes a strategy to produce circularly polarized thermally activated delayed fluorescence (CP-TADF). A set of two structurally similar organic emitters SFST and SFOT are constructed, whose spiro architectures containing asymmetric donors result in chirality. Upon grafting within the spiro frameworks, the donor and acceptor are fixed proximally in a face-to-face manner. This orientation allows intramolecular through-space charge transfer (TSCT) to occur in both emitters, leading to TADF properties. The donor units in SFST and SFOT have a sulfur and oxygen atom, respectively; such a subtle difference has great impacts on their photophysical, chiroptical, and electroluminescence (EL) properties. SFOT exhibits greatly enhanced EL performance in doped organic light-emitting diodes, with external quantum efficiency (EQE) up to 23.1%, owing to the concurrent manipulation of highly photoluminescent quantum efficiency (PLQY, ∼90%) and high exciton utilization. As a comparison, the relatively larger sulfur atom in SFST introduces heavy atom effects and leads to distortion of the molecular backbone that lengthens the donor-acceptor distance. SFST thus has lower PLQY and faster nonradiative decay rate. The collective consequence is that the EQE value of SFST, i.e., 12.5%, is much lower than that of SFOT. The chirality of these two spiro emitters results in circularly polarized luminescence. Because SFST has a more distorted molecular architecture than SFOT, the luminescence dissymmetry factor (|glum|) of circularly polarized luminescence of one enantiomer of the former, namely, either (S)-SFST or (R)-SFST, is almost twice that of (S)-SFOT/(R)-SFOT. Moreover, the CP organic light-emitting diodes (CP-OLEDs) show obvious circularly polarized electroluminescence (CPEL) signals with gEL of 1.30 × 10-3 and 1.0 × 10-3 for (S)-SFST and (S)-SFOT, respectively.

Highly Efficient Thermally Activated Delayed Fluorescence via an Unconjugated Donor-Acceptor System Realizing EQE of Over 30.

In this work, two novel thermally activated delayed fluorescence (TADF) emitters, 2tDMG and 3tDMG, are synthesized for high-efficiency organic light-emitting diodes (OLEDs), The two emitters have a tilted face-to-face alignment of donor (D)/acceptor (A) units presenting intramolecular noncovalent interactions. The two TADF materials are deposited either by an evaporation-process or by a solution-process, both of them leading to high OLED performance. 2tDMG used as the emitter in evaporation-processed OLEDs achieves a high external quantum efficiency (EQE) of 30.8% with a very flat efficiency roll-off of 7% at 1000 cd m-2 . The solution-processed OLEDs also display an interesting EQE of 16.2%. 3tDMG shows improved solubility and solution processability as compared to 2tDMG, and thus a high EQE of 20.2% in solution-processed OLEDs is recorded. The corresponding evaporation-processed OLEDs also reach a reasonably high EQE of 26.3%. Encouragingly, this work provides a novel strategy to address the imperious demands for OLEDs with high EQE and low roll-off.

Sky-Blue Thermally Activated Delayed Fluorescence with Intramolecular Spatial Charge Transfer Based on a Dibenzothiophene Sulfone Emitter.

Intramolecular spatial charge transfer (ISCT) plays a critical role in determining the optical and charge transport properties of thermally activated delayed fluorescence (TADF) materials. Herein, a new donor/acceptor-type TADF compound based on rigid dibenzothiophene sulfone (DBTS) moiety, STF-DBTS, was designed and synthesized. Fluorene unit was used as a rigid linker to position the rigid acceptor and donor subunit in close vicinity with control over their spacing and molecular structure and to achieve high photoluminescence quantum yield (∼53%) and TADF property. For comparison purposes, we constructed the more flexible STF-DPS with a less rotationally constrained diphenylsulphone (DPS) acceptor instead of the rigid DBTS units, and STF-DPS showed no TADF properties and lower PLQY (16.0%). Organic light-emitting diodes (OLEDs) based on STF-DBTS achieve an external quantum efficiency (EQE) of 10.3% at 488 nm, which is a fivefold improvement in EQE with respect to STF-DPS.

Near-Infrared Electroluminescence beyond 800†nm with High Efficiency and Radiance from Anthracene Cored Emitters.

Derivatives based on anthryleno[1,2-b]pyrazine-2,3-dicarbonitrile (DCPA) are used as luminescent materials, to realize near-infrared (NIR) electroluminescence. By functionalizing DCPA with aromatic amine donors, two emitters named DCPA-TPA and DCPA-BBPA are designed and synthesized. Both molecules have large dipole moments owing to the strong intramolecular charge transfer interactions between the amine donors and the DCPA acceptor. Thus, compared with doped films, the emission of neat films of DCPA-TPA and DCPA-BBPA can fully fall into the NIR region (>700 nm) with increasing surrounding polarity by increasing doping ratio. Moreover, the non-doped devices based on DCPA-TPA and DCPA-BBPA provide NIR emission with peaks at 838 and 916 nm, respectively. A maximum radiance of 20707 mW Sr-1 m-2 was realized for the further optimized device based on DCPA-TPA. This work provides a simple and efficient strategy of molecular design for developing NIR emitting materials.

Evolution of pure hydrocarbon hosts: simpler structure, higher performance and universal application in RGB phosphorescent organic light-emitting diodes.

In the field of phosphorescent organic light-emitting diodes (PhOLEDs), designing high-efficiency universal host materials for red, green and blue (RGB) phosphors has been quite a challenge. To date, most of the high-efficiency universal hosts reported incorporate heteroatoms, which have a crucial role in the device performance. However, the introduction of different kinds of heterocycles increases the design complexity and cost of the target material and also creates potential instability in the device performance. In this work, we show that pure aromatic hydrocarbon hosts designed with the 9,9'-spirobifluorene scaffold are high-efficiency and versatile hosts for PhOLEDs. With external quantum efficiencies of 27.3%, 26.0% and 27.1% for RGB PhOLEDs respectively, this work not only reports the first examples of high-efficiency pure hydrocarbon materials used as hosts in RGB PhOLEDs but also the highest performance reported to date for a universal host (including heteroatom-based hosts). This work shows that the PHC design strategy is promising for the future development of the OLED industry as a high-performance and low-cost option.

Optimization of Low-Dimensional Components of Quasi-2D Perovskite Films for Deep-Blue Light-Emitting Diodes.

Compared to efficient green and near-infrared light-emitting diodes (LEDs), less progress has been made on deep-blue perovskite LEDs. They suffer from inefficient domain [various number of PbX6 - layers (n)] control, resulting in a series of unfavorable issues such as unstable color, multipeak profile, and poor fluorescence yield. Here, a strategy involving a delicate spacer modulation for quasi-2D perovskite films via an introduction of aromatic polyamine molecules into the perovskite precursor is reported. With low-dimensional component engineering, the n1 domain, which shows nonradiative recombination and retarded exciton transfer, is significantly suppressed. Also, the n3 domain, which represents the population of emission species, is remarkably increased. The optimized quasi-2D perovskite film presents blue emission from the n3 domain (peak at 465 nm) with a photoluminescence quantum yield (PLQY) as high as 77%. It enables the corresponding perovskite LEDs to deliver stable deep-blue emission (CIE (0.145, 0.05)) with an external quantum efficiency (EQE) of 2.6%. The findings in this work provide further understanding on the structural and emission properties of quasi-2D perovskites, which pave a new route to design deep-blue-emissive perovskite materials.

Eco-Friendly Superwetting Material for Highly Effective Separations of Oil/Water Mixtures and Oil-in-Water Emulsions.

Because the treatment of oily wastewater, generated from many industrial processes, has become an increasing environmental concern, the search continues for simple, inexpensive, eco-friendly, and readily scalable processes for fabricating novel materials capable of effective oil/water separation. In this study we prepared an eco-friendly superhydrophilic and underwater superoleophobic polyvinylpyrrolidone (PVP)-modified cotton that mediated extremely efficient separations of mixtures of oil/water and oil/corrosive solutions. This PVP-modified cotton exhibited excellent antifouling properties and could be used to separate oil/water mixtures continuously for up to 20 h. Moreover, the compressed PVP-modified cotton could separate both surfactant-free and -stabilized oil-in-water emulsions with fluxes of up to 23,500 L m-2 h-1 bar-1-a level one to two orders of magnitude higher than that possible when using traditional ultrafiltration membranes having similar rejection properties. The high performance of our PVP-modified cotton and its green, low-energy, cost-effective preparation suggest its great potential for practical applications.

[The role of BCP in electroluminescence of multilayer organic light-emitting devices].

As a hole-blocking layer, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) is usually used in blue and white light electroluminescent devices. The ability of blocking holes of BCP layer depends on its thickness, and basically holes can tunnel through thin BCP layer. In order to know the role of BCP layer in electroluminescence (EL) of multilayer organic light-emitting diodes (OLEDs), in the present paper, the authors designed a multilayer OLED ITO/NPB/BCP/Alq3 : DCJTB/Alq3/Al and investigated the influence of thickness of BCP on the EL spectra of multilayer OLEDs at different applied voltages. The experimental data show that thin BCP layer can block holes partially and tune the energy transfer between different emissive layers, and in this way, it is easy to obtain white emission, but its EL spectra will change with the applied voltages. The EL spectra of multilayer device will remain relatively stable when BCP layer is thick enough, and the holes can hardly tunnel through when the thickness of BCP layer is more than 15 nm. Furthermore, the stability of EL spectra of the multilayer OLED at different applied voltages was discussed.

[Cathodoluminescent characteristics of green-emitting ZnAl2O4:Mn thin film phosphors].

Green electroluminescence was obtained from thin films of ZnAl2O4: Mn prepared by rf magnetron sputtering onto thick insulating ceramic sheets. Photoluminescence and stress-stimulated luminescence was obtained for Mn-doped ZnAl2O4 powder synthesized by the solid phase reaction. Since it is extremely stable chemically and thermally, ZnAl2O4 may emerge as an alternative choice to sulphide-based phosphors. In the present paper, thin films of ZnAl2O4: Mn were grown on aluminosilicate ceramic plates using spray pyrolysis of aqueous solutions. The cathodoluminescence (CL) properties of the films under low to medium excitation voltage (<5 kV) were investigated. The films exhibited green CL after being annealed at temperatures above 550 degrees C, which corresponds to the transition between 4 T1 and (6)A1 of Mn2+ ions located in the tetra coordination of the Zn2+ site in the spinel structure. The chromaticity coordinates were x = 0.150 and y = 0.734 with a dominant wavelength of 525 nm and an 82% color purity. The CL luminance and efficiency depended on the excitation voltage and current density. Saturation effects were observed as the current density increased. A luminance of 540 cd x m(-2) and an efficiency of 4.5 lm x W(-1) were obtained at an excitation voltage of 4 kV with a current density of 38 microA x cm(-2).