Structure Engineering of Acridine Donor to Optimize Color Purity of Blue Thermally Activated Delayed Fluorescence Emitters.

9,9-Dimethyl-9,10-dihydroacridine (DMAC) is one of the most widely used electron donor for constructing high-performance thermally activated delayed fluorescence (TADF) emitters. However, DMAC-based emitters often suffer from the imperfect color purity, particularly in blue emitters, due to its strong electron-donating capability. To modulate donor strength, 2,7-F-Ph-DMAC and 2,7-CF3-Ph-DMAC were designed by introducing the electron-withdrawing 2-fluorophenyl and 2-(trifluoromethyl)phenyl at the 2,7-positions of DMAC. These donors were used, in combination with 2,4,6-triphenyl-1,3,5-triazine (TRZ) acceptor, to develop novel TADF emitters 2,7-F-Ph-DMAC-TRZ and 2,7-CF3-Ph-DMAC-TRZ. Compared to the F- or CF3-free reference emitter, both two emitters showed hypsochromic effect in fluorescence and comparable photoluminescence quantum yields without sacrificing the reverse intersystem crossing rate constants. In particular, 2,7-CF3-Ph-DMAC-TRZ based OLED exhibited a blue shift by up to 39 nm and significantly improved Commission International de l'Éclairage (CIE) coordinates from (0.36, 0.55) to (0.22, 0.41), while the external quantum efficiency kept stable at about 22.5 %. This donor engineering strategy should be valid for improving the color purity of large amount of acridine based TADF emitters. It can be predicted that pure blue TADF emitters should be feasible if these F- or CF3-modifed acridine donors are combined with other weaker electron acceptors.

High-Efficiency and Narrowband Green Thermally Activated Delayed Fluorescence Organic Light-Emitting Diodes Based on Two Diverse Boron Multi-Resonant Skeletons.

Up to now, highly efficient narrowband thermally activated delayed fluorescence (TADF) molecules constructed by oxygen-bridged boron with an enhancing multiple resonance (MR) effect have been in urgent demand for solid-state lighting and full-color displays. In this work, a novel MR-TADF molecule, BNBO, constructed by the oxygen-bridged boron unit and boron-nitrogen core skeleton as an electron-donating moiety, is successfully designed and synthesized via a facile one-step synthesis. Based on BNBO as an efficient green emitter, the organic light-emitting diode (OLED) shows a sharp emission peak of 508 nm with a full-width at half-maximum (FWHM) of 36 nm and realizes quite high peak efficiency values, including an external quantum efficiency (EQEmax) of 24.3% and a power efficiency (PEmax) of 62.3 lm/W. BNBO possesses the intramolecular charge transfer (ICT) property of donor-acceptor (D-A) materials and multiple resonance characteristics, which provide a simple strategy for narrowband oxygen-boron materials.

Exploring the Electroluminescent Applications of Imidazole Derivatives.

Recently, the fields of organic light-emitting diodes (OLEDs) and light-emitting electrochemical cells (LECs) have improved tremendously with regard to tunable emission, efficiency, brightness, and thermal stability. Imidazole derivatives are excellent deep blue-green light-emitting layers in the OLED or LEC devices. This Review summarizes the major breakthroughs of various electroluminescence (EL) layers with imidazole-containing organic or organometallic derivatives, the molecular design principles, and their light-emitting performances as effective EL materials. The highly tunable chemical structures and flexible molecular design strategies of imidazole-based compounds are advantages that provide great opportunities for researchers. They can provide a good basis for the design and development of new EL materials with narrower emission and higher efficiency. Moreover, imidazole compounds have demonstrated breakthrough performances in thermally activated delayed fluorescence (TADF) properties where triplet excitons are utilized to inhibit anti-intersystem quenching, showing great promise in breaking the theoretical external quantum efficiencies (EQE) limits in traditional fluorescent devices.

Carbonyl-Containing Thermally Activated Delayed Fluorescence Emitters for Narrow-Band Electroluminescence.

Carbonyl-containing derivatives show enduring vitality in the field of thermally activated delayed fluorescence (TADF) materials; they can realize high device efficiency by using both singlet and triplet excitons for electroluminescence. Recently, a system based on fused ketone/amine exhibited huge potential for constructing multi-resonance TADF (MR-TADF) emitters, which exhibit higher narrow-band emission than conventional TADF emitters with twisted donor-acceptor (D-A) structure. Herein, we summarize current research progress in both traditional and MR-type ketone derivatives with TADF characteristics for introducing the molecular design strategy of maintaining high device efficiency while keeping narrow-band emission profile. We hope this review can inspire the emergence of more high-performance narrow-band materials.

Intrinsically Stretchable Electroluminescent Elastomers with Self-Confinement Effect for Highly Efficient Non-Blended Stretchable OLEDs.

Ultra-flexible stretchable organic light-emitting diodes (OLEDs) are emerging as a basic component of flexible electronics and human-machine interfaces. However, the brightness and efficiency of stretchable OLEDs remain still far inferior to their rigid counterparts, owing to the scarcity of satisfactory stretchable electroluminescent materials. Herein, we explore a general concept based on the self-confinement effect to dramatically improve the stretchability of elastomers, without affecting electroluminescent properties. The balanced rigid/flexible chain dynamics under self-confinement significantly reduces the modulus of the elastomers, resulting in the maximum strain reaching 806 %. Ultra-flexible stretchable OLEDs have been constructed based on the resulting ISEEs, achieving unprecedented high-performance non-blended stretchable OLEDs. The results suggest an effective molecular design strategy for highly deformable stretchable displays and flexible electronics.

New-Fashioned Universal and Functional Host-Material from a Near-Ultraviolet Organic Emitter for High-Efficiency Organic Light-Emitting Diodes with Low Efficiency Roll-Offs.

In this work, a near-ultraviolet (NUV) emitter, 2MCz-CNMCz, with hot-exciton property is designed based on a "long-short axis" strategy, which exhibits good thermal stability, bipolar carrier transport ability, and high T1 energy level. Its nondoped NUV organic light-emitting diode (OLED) achieves a record maximum external quantum efficiency (ηext ) of 7.76%, with a peak at 404 nm and CIE coordinates of (0.158, 0.039). The corresponding high exciton utilization efficiency (ηr ) in the electroluminescence process reveals its potential as a functional sensitizing host. As expected, the TBPe-based blue fluorescent OLED with 2MCz-CNMCz as the host material shows better efficiency and lower efficiency roll-off than that with traditional host material mCP. Meanwhile, the Ir complexes-based green/yellow/red phosphorescent OLEDs with 2MCz-CNMCz host are also fabricated, reaching high ηext values of 26.1%, 30.4%, and 20.4%, respectively, and displaying negligible efficiency roll-offs at 1000 cd m-2 , which are among the best OLED performances based on the same emitters. To the authors' best knowledge, this is the first report on the design of high-quality universal and functional host material, and may bring new inspiration to the preparation of high-efficiency, low roll-off, full-color OLEDs.

Optimizing Intermolecular Interactions and Energy Level Alignments of Red TADF Emitters for High-Performance Organic Light-Emitting Diodes.

Adequately harvesting all excitons in a single molecule and inhibiting exciton losses caused by intermolecular interactions are two important factors for achieving high efficiencies thermally activated delayed fluorescence (TADF). One potential approach for optimizing these is to tune alignment of various excited state energy levels by using different doping concentrations. Unfortunately, emission efficiencies of most TADF emitters decrease rapidly with concentrations which limits the window for energy level tunning. In this work, by introducing a spiro group to increase steric hindrance of a TADF emitter (BPPXZ) with a phenoxazine and a dibenzo[a,c]phenazine, emission efficiency of the resulting molecule (BPSPXZ) is much less affected by concentration increase. This enables exploitation of the concentration effects to tune energy levels of its excited states for obtaining simultaneously small singlet-triplet energy offset and large spin-orbital coupling, leading to high-efficiency reverse intersystem crossing. With these merits, organic light-emitting diodes (OLEDs) using the BPSPXZ emitter from 5 to 60 wt% doping can all deliver EQE of over 20%. More importantly, record-high EQEs of 33.4% and 15.8% are respectively achieved in the optimized and nondoped conditions. This work proposes a strategy for developing red TADF emitters by optimizing the intermolecular interaction and energy level alignments to facilitate exciton utilization over wide doping concentrations.

Deep-Red and Near-Infrared Iridium Complexes with Fine-Tuned Emission Colors by Adjusting Trifluoromethyl Substitution on Cyclometalated Ligands Combined with Matched Ancillary Ligands for Highly Efficient Phosphorescent Organic Light-Emitting Diodes.

Six novel Ir(C^N)2(L^X)-type heteroleptic iridium complexes with deep-red and near-infrared region (NIR)-emitting coverage were constructed through the cross matching of various cyclometalating (C^N) and ancillary (LX) ligands. Here, three novel C^N ligands were designed by introducing the electron-withdrawing group CF3 on the ortho (o-), meta (m-), and para (p-) positions of the phenyl ring in the 1-phenylisoquinoline (piq) group, which were combined with two electron-rich LX ligands (dipba and dipg), respectively, leading to subsequent iridium complexes with gradually changing emission colors from deep red (≈660 nm) to NIR (≈700 nm). Moreover, a series of phosphorescent organic light-emitting diodes (PhOLEDs) were fabricated by employing these phosphors as dopant emitters with two doping concentrations, 5% and 10%, respectively. They exhibited efficient electroluminescence (EL) with significantly high EQE values: >15.0% for deep red light0 (λmax = 664 nm) and >4.0% for NIR cases (λmax = 704 nm) at a high luminance level of 100 cd m-2. This work not only provides a promising approach for finely tuning the emission color of red phosphors via the easily accessible molecular design strategy, but also enables the establishment of an effective method for enriching phosphorescent-emitting molecules for practical applications, especially in the deep-red and near-infrared region (NIR).

Two-Dimensionally Stretchable Organic Light-Emitting Diode with Elastic Pillar Arrays for Stress Relief.

Recent advanced studies on flexible and stretchable electronic devices and optoelectronics have made possible a variety of soft and more functional electronic devices. With consumer demand for highly functional or free-form displays, high flexibility and stretchability in light-emitting devices are needed. Herein, we developed a unique structure of stretchable substrates with pillar arrays to reduce the stress on the active area of devices when strain is applied. We confirmed the advantages of the produced structures using mechanical simulation tools and determined that the structures effectively lessen the applied stress of interconnection as well as the active area in a stretched state. With this stress-relief stretchable substrate, we realized stretchable OLEDs that are compliant and maintain their performance under high strain deformation. Also, devices can be stretched in the biaxis, which is superior to only one-directional stretchable electronics; as such, devices can be used in practical applications like wearable electronics and health monitoring systems. We propose, for the first time, stretchable OLEDs patterned by the thermal evaporation fabrication process onto stress-relief substrates. These OLEDs can mitigate certain problems in previous studies of stretchable OLEDs without need to find new materials or to use a prestrained fabrication process.

Theoretical Studies of Photophysical Properties of D-π-A-π-D-Type Diketopyrrolopyrrole-Based Molecules for Organic Light-Emitting Diodes and Organic Solar Cells.

A series of D-π-A diketopyrrolopyrrole(DPP)-based small molecules were designed for organic light-emitting diode(OLEDs) and organic solar cell(OSCs) applications. Applying the PBE0/6-31G(d,p) method, the ground state geometry and relevant electronic properties were investigated. The first excited singlet state geometry and the absorption and fluorescent spectra were simulated at the TD-PBE0/6-31G(d,p) level. The calculated results revealed that the photophysical properties were affected through the introduction of different end groups. Furthermore, the electronic transitions corresponding to absorption and emission exhibited an intramolecular charge transfer feature. Our results suggest that the designed molecules acted not only as luminescent for OLEDs, but also as donor materials in OSCs. Moreover, they can also be used as potential electron transfer materials for OLEDs and OSCs.

Monodisperse Six-Armed Starbursts based on Truxene-Cored Multibranched Oligofluorenes: Design, Synthesis, and Stabilized Lasing Characteristics.

A series of monodisperse six-armed conjugated starbursts (Tr1F, Tr2F, and Tr3F) containing a truxene core and multibranched oligofluorene bridges capped with diphenylamine (DPA) units has been designed, synthesized, and investigated as robust gain media for organic semiconductor lasers (OSLs). The influence of electron-rich DPA end groups on their optoelectronic characteristics has been discussed at length. DPA cappers effectively raise HOMO levels of the starbursts, thus enhancing the hole injection and transport ability. Solution-processed electroluminescence devices based on the resulting six-armed starbursts exhibited efficient deep-blue electroluminescence with clear reduced turn-on voltages (3.2-3.5 V). Moreover, the resulting six-armed molecules showed stabilized electroluminescence and amplified spontaneous emission with low thresholds (27.4-63.9 nJ pulse-1 ), high net gain coefficients (80.1-101.3 cm-1 ), and small optical loss (2.6-4.4 cm-1 ). Distributed feedback OSLs made from Tr3F exhibited a low lasing threshold of 0.31 kW cm-2 (at 465 nm). The results suggest that the construction of truxene-centered six-armed conjugated starbursts with the incorporation of DPA units can effectively enhance EL properties by precisely regulating the HOMO energy levels, and further optimizing their optical gain properties.

Recent Advances in the Optimization of Organic Light-Emitting Diodes with Metal-Containing Nanomaterials.

Metal-containing nanomaterials have attracted widespread attention in recent years due to their physicochemical, light-scattering and plasmonic properties. By introducing different kinds and different structures of metal-containing nanomaterials into organic light-emitting diodes (OLEDs), the optical properties of the devices can be tailored, which can effectively improve the luminous efficiency of OLEDs. In this review, the fundamental knowledge of OLEDs and metallic nanomaterials were firstly introduced. Then we overviewed the recent development of the optimization of OLEDs through introducing different kinds of metal-containing nanomaterials.

Adamantane-Substituted Acridine Donor for Blue Dual Fluorescence and Efficient Organic Light-Emitting Diodes.

To date, blue dual fluorescence emission (DFE) has not been realized because of the limited choice of chemical moieties and severe geometric deformation of the DFE emitters leading to strong intramolecular charge transfer (ICT) with a large Stokes shift in excited states. Herein, an emitter (1'r,5'R,7'S)-10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-10H-spiro [acridine-9,2'-adamantane] (a-DMAc-TRZ) containing a novel adamantane-substituted acridine donor is reported, which exhibits unusual blue DFE. The introduction of the rigid and bulky adamantane moiety not only suppressed the geometry relaxation in excited state, but also induced the formation of quasi-axial conformer (QAC) and quasi-equatorial conformer (QEC) geometries, leading to deep-blue conventional fluorescence and sky-blue thermally activated delayed fluorescence (TADF). The resulting organic light-emitting diodes (OLEDs) achieved a maximum external quantum efficiency (EQE) of about 29 %, which is the highest reported for OLEDs based on dual-conformation emitters.

Calixarenes as High Temperature Matrices for Thermally Activated Delayed Fluorescence: C70 in Dihomooxacalix[4]arene.

Thermally activated delayed fluorescence (TADF) of 12C70 and 13C70 was observed up to 140 °C in a p-tert-butyldihomooxacalix[4]arene solid matrix, a temperature range significantly higher than that of previous TADF quantitative studies. An effective singlet-triplet energy gap of 29 kJ/mol and triplet formation quantum yields of 0.97 and 0.99 were measured for 12C70 and 13C70, respectively. The photophysical properties of the two fullerenes in this new matrix are comparable to those obtained in polystyrene at a lower temperature range. Calixarenes are proposed to be suitable matrices for high temperature TADF studies and applications.

Theoretical Investigations of the Photophysical Properties of Star-Shaped π-Conjugated Molecules with Triarylboron Unit for Organic Light-Emitting Diodes Applications.

The density functional theory (DFT) and time-dependent DFT (TD-DFT) methodologies have been applied to explore on a series of star-shaped π-conjugated organoboron systems for organic light-emitting diode (OLED) materials. The compounds under investigation consist of benzene as π-bridge and different core units and triarylboron end groups. Their geometry structures, frontier molecular orbital (FMO) energies, absorption and fluorescence spectra, and charge transport properties have been investigated systematically. It turned out that the FMO energy levels, the band gaps, and reorganization energies optical are affected by the introduction of different core units and triarylboron end groups. The results suggest that the designed compounds are expected to be promising candidates for luminescent materials. Furthermore, they can also serve as hole and/or electron transport materials for OLEDs.

Phosphorescent Platinum(II) Complexes with Mesoionic 1H-1,2,3-Triazolylidene Ligands.

The synthesis and characterization of eight unprecedented phosphorescent C^C* cyclometalated mesoionic aryl-1,2,3-triazolylidene platinum(II) complexes with different ß-diketonate ligands are reported. All compounds proved to be strongly emissive at room temperature in poly(methyl methacrylate) films with an emitter concentration of 2 wt %. The observed photoluminescence properties were strongly dependent on the substitution on the aryl system and the ß-diketonate ligand. Compared to acetylacetonate, the ß-diketonates with aromatic substituents (mesityl and duryl) were found to significantly enhance the quantum yield while simultaneously reducing the emission lifetimes. Characterization was carried out by standard techniques, as well as solid-state structure determination, which confirmed the binding mode of the carbene ligand. DFT calculations, carried out to predict the emission wavelength with maximum intensity, were in excellent agreement with the (later) obtained experimental data.

Palladium-Catalyzed N-Arylation of Iminodibenzyls and Iminostilbenes with Aryl- and Heteroaryl Halides.

Compounds containing the iminodibenzyl and iminostilbene ring systems are prevalent in medicinal targets and functional materials. Herein, we report palladium-catalyzed conditions for the N-arylation of these ring systems. This protocol could be applied to a variety of (hetero)aryl chloride and bromide substrates, including ones, which are sterically hindered or those containing a variety of functional groups. Use of the fourth-generation palladacycle precatalyst gave good to excellent yields by using low palladium-catalyst loadings (0.1 to 1 mol %).

Towards Printed Organic Light-Emitting Devices: A Solution-Stable, Highly Soluble CuI -NHetPHOS.

The development of iridium-free, yet efficient emitters with thermally activated delayed fluorescence (TADF) was an important step towards mass production of organic light-emitting diodes (OLEDs). Progress is currently impeded by the low solubility and low chemical stability of the materials. Herein, we present a CuI -based TADF emitter that is sufficiently chemically stable under ambient conditions and can be processed by printing techniques. The solubility is drastically enhanced (to 100 g L-1 ) in relevant printing solvents. The integrity of the complex is preserved in solution, as was demonstrated by X-ray absorption spectroscopy and other techniques. In addition, it was found that the optoelectronic properties are not affected even when partly processing under ambient conditions. As a highlight, we present a TADF-based OLED device that reached an efficiency of 11±2 % external quantum efficiency (EQE).

Novel red phosphorescent polymers bearing both ambipolar and functionalized Ir(III) phosphorescent moieties for highly efficient organic light-emitting diodes.

A series of novel red phosphorescent polymers is successfully developed through Suzuki cross-coupling among ambipolar units, functionalized Ir(III) phosphorescent blocks, and fluorene-based silane moieties. The photophysical and electrochemical investigations indicate not only highly efficient energy-transfer from the organic segments to the phosphorescent units in the polymer backbone but also the ambipolar character of the copolymers. Benefiting from all these merits, the phosphorescent polymers can furnish organic light-emitting diodes (OLEDs) with exceptional high electroluminescent (EL) efficiencies with a current efficiency (η L ) of 8.31 cd A(-1) , external quantum efficiency (η ext ) of 16.07%, and power efficiency (η P ) of 2.95 lm W(-1) , representing the state-of-the-art electroluminescent performances ever achieved by red phosphorescent polymers. This work here might represent a new pathway to design and synthesize highly efficient phosphorescent polymers.

Photodynamic therapy offers a novel approach to managing miltefosine-resistant cutaneous leishmaniasis.

Cutaneous leishmaniasis (CL) is a neglected disease caused by Leishmania parasites. The oral drug miltefosine is effective, but there is a growing problem of drug resistance, which has led to increasing treatment failure rates and relapse of infections. Photodynamic therapy (PDT) combines a light source and a photoactive drug to promote cell death by oxidative stress. Although PDT is effective against several pathogens, its use against drug-resistant Leishmania parasites remains unexplored. Herein, we investigated the potential of organic light-emitting diodes (OLEDs) as wearable light sources, which would enable at-home use or ambulatory treatment of CL. We also assessed its impact on combating miltefosine resistance in Leishmania amazonensis-induced CL in mice. The in vitro activity of OLEDs combined with 1,9-dimethyl-methylene blue (DMMB) (OLED-PDT) was evaluated against wild-type and miltefosine-resistant L. amazonensis strains in promastigote (EC50 = 0.034 µM for both strains) and amastigote forms (EC50 = 0.052 µM and 0.077 µM, respectively). Cytotoxicity in macrophages and fibroblasts was also evaluated. In vivo, we investigated the potential of OLED-PDT in combination with miltefosine using different protocols. Our results demonstrate that OLED-PDT is effective in killing both strains of L. amazonensis by increasing reactive oxygen species and stimulating nitric oxide production. Moreover, OLED-PDT showed great antileishmanial activity in vivo, allowing the reduction of miltefosine dose by half in infected mice using a light dose of 7.8 J/cm2 and 15 µM DMMB concentration. In conclusion, OLED-PDT emerges as a new avenue for at-home care and allows a combination therapy to overcome drug resistance in cutaneous leishmaniasis.