RESUMO
A novel series of excited-state intramolecular proton transfer (ESIPT) emitters, namely, DPNA, DPNA-F, and DPNA-tBu, endowed with dual intramolecular hydrogen bonds, were designed and synthesized. In the condensed phase, DPNAs exhibit unmatched absorption and emission spectral features, where the minor 0-0 absorption peak becomes a major one in the emission. Detailed spectroscopic and dynamic approaches conclude fast ground-state equilibrium among enol-enol (EE), enol-keto (EK), and keto-keto (KK) isomers. The equilibrium ratio can be fine-tuned by varying the substitutions in DPNAs. Independent of isomers and excitation wavelength, ultrafast ESIPT takes place for all DPNAs, giving solely KK tautomer emission maximized at >650 nm. The spectral temporal evolution of ESIPT was resolved by a state-of-the-art technique, namely, the transient grating photoluminescence (TGPL), where the rate of EK* â KK* is measured to be (157 fs)-1 for DPNA-tBu, while a stepwise process is resolved for EE* â EK* â KK*, with a rate of EE* â EK* of (72 fs)-1. For all DPNAs, the KK tautomer emission shows a narrowband emission with high photoluminescence quantum yields (PLQY, â¼62% for DPNA in toluene) in the red, offering advantages to fabricate deep-red organic light-emitting diodes (OLED). The resulting OLEDs give high external quantum efficiency with a spectral full width at half-maximum (FWHM) as narrow as â¼40 nm centered at 666-670 nm for DPNAs, fully satisfying the BT. 2020 standard. The unique ESIPT properties and highly intense tautomer emission with a small fwhm thus establish a benchmark for reaching red narrowband organic electroluminescence.
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The adverse aggregated-caused quenching (ACQ) problem of most electroluminescent materials existing in highly doped thin films is one of the key factors impeding the commercialization of high-efficiency organic light-emitting diodes (OLEDs) panel. Whereas, by delicately constructing and modulating moderate intermolecular interactions, some aggregates have been demonstrated to present distinct luminescent properties such as tunable emission spectra, improved photoluminescence quantum yields, different emission mechanism and enhanced horizontal transition dipole ratio (Θ) of emitting layer, providing feasible solution for ACQ problem. The luminescence from newly generated emissive state in aggregates is different from the traditional "isolated" molecules in organic electronics and will possess novel properties and applications. Herein, we summarize the different types of intermolecular interactions within emitter aggregates exhibiting distinct luminescent mechanisms, as well as their effects on photoluminescent and electroluminescent properties, offering reliable reference for the advancement of highly efficient OLEDs utilizing aggregated emitters.
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Currently, much research effort has been devoted to improving the exciton utilization efficiency and narrowing the emission spectra of ultraviolet (UV) fluorophores for organic light-emitting diode (OLED) applications, while almost no attention has been paid to optimizing their light out-coupling efficiency. Here, we developed a linear donor-acceptor-donor (D-A-D) triad, namely CDFDB, which possesses high-lying reverse intersystem crossing (hRISC) property. Thanks to its integrated narrowband UV photoluminescence (PL) (λPL: 397â nm; FWHM: 48â nm), moderate PL quantum yield (ÏPL: 72 %, Tol), good triplet hot exciton (HE) conversion capability, and large horizontal dipole ratio (Θ//: 92 %), the OLEDs based on CDFDB not only can emit UV electroluminescence with relatively good color purity (λEL: 398â nm; CIEx,y: 0.161, 0.040), but also show a record maximum external quantum efficiency (EQEmax) of 12.0 %. This study highlights the important role of horizontal dipole orientation engineering in the molecular design of HE UV-OLED fluorophores.
RESUMO
Herein, we propose a regional functionalization molecular design strategy that enables independent control of distinct pivotal parameters through different molecule segments. Three novel multiple resonances thermally activated delayed fluorescence (MR-TADF) emitters A-BN, DA-BN, and A-DBN, have been successfully synthesized by integrating highly rigid and three-dimensional adamantane-containing spirofluorene units into the MR framework. These molecules form two distinctive functional parts: partâ 1 comprises a boron-nitrogen (BN)-MR framework with adjacent benzene and fluorene units forming a central luminescent core characterized by an exceptionally rigid planar geometry, allowing for narrow FWHM values; partâ 2 includes peripheral mesitylene, benzene, and adamantyl groups, creating a unique three-dimensional "umbrella-like" conformation to mitigate intermolecular interactions and suppress exciton annihilation. The resulting A-BN, DA-BN, and A-DBN exhibit remarkably narrow FWHM values ranging from 18 to 14â nm and near-unity photoluminescence quantum yields. Particularly, OLEDs based on DA-BN and A-DBN demonstrate outstanding efficiencies of 35.0 % and 34.3 %, with FWHM values as low as 22â nm and 25â nm, respectively, effectively accomplishing the integration of high color purity and high device performance.
RESUMO
Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials hold great promise for advanced high-resolution organic light-emitting diode (OLED) displays. However, persistent challenges, such as severe aggregation-caused quenching (ACQ) and slow spin-flip, hinder their optimal performance. We propose a synergetic steric-hindrance and excited-state modulation strategy for MR-TADF emitters, which is demonstrated by two blue MR-TADF emitters, IDAD-BNCz and TIDAD-BNCz, bearing sterically demanding 8,8-diphenyl-8H-indolo[3,2,1-de]acridine (IDAD) and 3,6-di-tert-butyl-8,8-diphenyl-8H-indolo[3,2,1-de]acridine (TIDAD), respectively. These rigid and bulky IDAD/TIDAD moieties, with appropriate electron-donating capabilities, not only effectively mitigate ACQ, ensuring efficient luminescence across a broad range of dopant concentrations, but also induce high-lying charge-transfer excited states that facilitate triplet-to-singlet spin-flip without causing undesired emission redshift or spectral broadening. Consequently, implementation of a high doping level of IDAD-BNCz resulted in highly efficient narrowband electroluminescence, featuring a remarkable full-width at half-maximum of 34â nm and record-setting external quantum efficiencies of 34.3 % and 31.8 % at maximum and 100â cd m-2, respectively. The combined steric and electronic effects arising from the steric-hindered donor introduction offer a compelling molecular design strategy to overcome critical challenges in MR-TADF emitters.
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Purely organic compounds served as promising materials for organic electronics have intrigued extensive research focuses owing to their unique photophysical and electronic properties. In the field of organic light-emitting diodes (OLEDs), the utilization of triplet excitons is of great significance for realizing high-performance devices. In contrast to the traditional aromatic amine-based counterparts, sulfur atom with a high-level outer orbit simultaneously provides powerful electron-donating ability and striking spin-orbit coupling effect to facilitate the utilization of theoretically spin-forbidden triplet excitons, demonstrating great prospect in constructing highly emissive purely organic emitters for OLED applications. Herein, we summarize the currently developed sulfur-decorated nonaromatic amine-based emitters exhibiting attractive photoelectronic characteristics, and gain insight into the understanding of molecular design and photophysical processes of these emitters, providing new perspectives for enriching the existing luminescent material systems and designing high-performance emitters.
RESUMO
Near-infrared (NIR) organic light-emitting diodes (OLEDs) suffer from the low external electroluminescence (EL) quantum efficiency (EQE), which is a critical obstacle for potential applications. Herein, 1-oxo-1-phenalene-2,3-dicarbonitrile (OPDC) is employed as an electron-withdrawing aromatic ring, and by incorporating with triphenylamine (TPA) and biphenylphenylamine (BBPA) donors, two novel NIR emitters with thermally activated delayed fluorescence (TADF) characteristics, namely OPDC-DTPA and OPDC-DBBPA, are first developed and compared in parallel. Intense NIR emission peaks at 962 and 1003â nm are observed in their pure films, respectively. Contributed by the local excited (LE) characteristics in the triplet (T1 ) state in synergy with the charge transfer (CT) characteristics for the singlet (S1 ) state to activate TADF emission, the solution processable doped NIR OLEDs based on OPDC-DTPA and OPDC-DBBPA yield EL peaks at 834 and 906â nm, accompanied with maximum EQEs of 0.457 and 0.103 %, respectively, representing the state-of-the-art EL performances in the TADF emitter-based NIR-OLEDs in the similar EL emission regions so far. This work manifests a simple and effective strategy for the development of NIR TADF emitters with long wavelength and efficiency synchronously.
RESUMO
Polychlorinated (hetero)arenes have shown great promise for organic optoelectronics applications. However, the harsh synthetic routes for polychlorinated compounds and the possible luminescence quenching from the compact intermolecular π-π stacking induced by chlorine atoms limit their investigations and applications in luminescent materials. Herein, two isomeric polychlorinated polycyclic aromatic hydrocarbon (PAH) compounds JY-1-Cl and JY-2-Cl consisting of rigidified aryl ketones and amine are designed and synthesized under mild conditions through nucleophilic chlorination intermediated by an electron donor-acceptor complex. Among them, as a result of the strong π-π interactions induced by chlorine atoms, JY-2-Cl exhibits bright monomer and dimer emissions with dual thermally activated delayed fluorescence (TADF) characters. Notably, compared with the non-chlorinated compounds, a high photoluminescence quantum yield is maintained after introducing multiple chlorine atoms into JY-2-Cl. The first dual-TADF organic light-emitting diodes are also successfully fabricated with maximum external quantum efficiency as high as 29.1 % by employing JY-2-Cl as emitter. This work presents a new paradigm and synthesis of polychlorinated amine-carbonyl PAHs and demonstrates the great potential of the chlorinated materials for luminescent applications.
RESUMO
Sulfone-embedded heterocyclics are of great interest in organic light-emitting diodes (OLEDs), however, exploring highly efficient narrowband emitters based on sulfone-embedded heterocyclics remains challenging. Herein, five emitters with different sulfur valence state and molecular rigidity, namely tP, tCPD, 2tCPD, tPD and tPT, are thoroughly analysed. With restricted twisting of flexible peripheral phenyl by strengthening molecular rigidity, molecular emission spectra can be enormously narrowed. Further, introducing the sulfone group with bending vibration in low-frequency region that suppresses high-frequency vibration, sharp narrow full-widths at half-maximum of 28 and 25â nm are achieved for 2tCPD and tPD, respectively. Maximum external quantum efficiencies of 22.0 % and 27.1 % are successfully realized for 2tCPD- and tPD-based OLED devices. These results offer a novel design strategy for constructing narrowband emitters by introducing sulfone group into a rigid molecular framework.
RESUMO
Although tremendous progress has recently been made in quasi-2D perovskite light-emitting diodes (PeLEDs), the performance of red PeLEDs emitting at ≈650-660 nm, which have wide prospects for application in photodynamic therapy, is still limited by an inefficient energy transfer process between the quasi-2D perovskite layers. Herein, a symmetric molecule of 3,3'-(9H-fluorene-9,9-diyl)dipropanamide (FDPA) is designed and developed with two functional acylamino groups and incorporated into the quasi-2D perovskites as the additive for achieving high-performance red PeLEDs. It is demonstrated that the agent can simultaneously diminish the van der Waals gaps between individual perovskite layers and passivate uncoordinated Pb2+ related defects at the surface and grain boundaries of the quasi-2D perovskites, which truly results in an efficient energy transfer in the quasi-2D perovskite films. Consequently, the red PeLEDs emitting at 653 nm with a peak external quantum efficiency of 18.5% and a maximum luminance of 2545 cd m-2 are achieved, which is among the best performing red quasi-2D PeLEDs emitting at ≈650-660 nm. This work opens a way to further improve the electroluminescence performance of red PeLEDs.
RESUMO
Aromatic imide derivatives play a critical role in boosting the electroluminescent (EL) performance of organic light-emitting diodes (OLEDs). However, the majority of aromatic imide-based materials are limited to long wavelength emission OLEDs rather than blue emissions due to their strong electron-withdrawing characteristics. Herein, two novel polycyclic fused amide units were reported as electron acceptor to be combined with either a tetramethylcarbazole or acridine donor via a phenyl linker to generate four conventional fluorescence blue emitters of BBI-4MeCz, BBI-DMAC, BSQ-4MeCz and BSQ-DMAC for the first time. BSQ-4MeCz and BSQ-DMAC based on a BSQ unit exhibited higher thermal stability and photoluminescence quantum yields than BBI-4MeCz and BBI-DMAC based on a BBI unit due to their more planar acceptor structure. The intermolecular interactions that exist in the BSQ series materials effectively inhibit the molecular rotation and configuration relaxation, and thus allow for blue-shifted emissions. Blue OLED devices were constructed with the developed materials as emitters, and the effects of both the structure of the polycyclic fused amide acceptor and the electron donor on the EL performance were clarified. Consequently, a sky-blue OLED device based on BSQ-DMAC was created, with a high maximum external quantum efficiency of 4.94% and a maximum luminance of 7761 cd m-2.
RESUMO
Multiple resonance thermally activated delayed fluorescence (MR-TADF) compounds have set off an upsurge of research because of their tremendous application prospects in the field of wide color gamut display. Herein, we propose a novel MR-TADF molecular construction paradigm based on polycyclization of the multiple resonance parent core, and construct a representative multiple resonance polycyclic aromatic hydrocarbon (MR-PAH) based on the para-alignment of boron and nitrogen atoms into a six-membered ring (p-BNR). Through the retrosynthesis analysis, a concise synthesis strategy with wide applicability has been proposed, encompassing programmed sequential boron esterification, Suzuki coupling and Scholl oxidative coupling. The target model molecule BN-TP shows green fluorescence with an emission peak at 523â nm and a narrow full-width at half-maximum (FWHM) of 34â nm. The organic light-emitting diode (OLED) employing BN-TP as an emitter exhibits ultrapure green emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.26, 0.70), and achieves a maximum external quantum efficiency (EQE) of 35.1 %.
RESUMO
A series of ultrapure-blue thermally activated delayed fluorescence (TADF) emitters featuring through-space charge transfer (TSCT) have been constructed by close stacking between the donor and acceptor moieties in rigid heteroaromatic compounds. The obviously accelerated radiative transition of singlet excitons, the diminished vibrionic relaxation of ground and excited states, and the consequent reduced Stokes shift and the narrow emission are evident. The corresponding organic light-emitting diodes (OLEDs) based on AC-BO realize the best performance among all deep-blue TSCT-TADF emitters, with an external quantum efficiency (EQEmax ) of 19.3 %. Furthermore, the OLEDs based on QAC-BO display an EQEmax of 15.8 %, and achieve the first high-efficiency ultrapure-blue TSCT-TADF material with an excellent Commission Internationale de L'Eclairage coordinate (CIE) of (0.145, 0.076) which perfectly matches the ultrapure-blue CIE requirements (0.14, 0.08) defined by the National Television System Committee.
RESUMO
Highly efficient organic thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) emitters for organic light-emitting diodes (OLEDs) generally consist of a twisted donor-acceptor skeleton with aromatic amine donors. Herein, through introducing sulfur atoms into isomeric pentaphene and pentacene frameworks, we demonstrate a set of polycyclic luminophores exhibiting efficient TADF and RTP characters. The incorporation of sulfur atoms confirms a folded molecular plane, while intensifies singlet-triplet spin-orbit coupling. Further, the isomeric effect has a significant effect on the electronic structure of excited state, giving rise to the investigated compounds tunable luminescence mechanisms of TADF and RTP. With efficient triplet harvesting ability, maximum external quantum efficiencies up to 25.1 % and 8.7 % are achieved for the corresponding TADF and RTP OLEDs, verifying the great potential of sulfur-bridged frameworks for highly efficient devices.
RESUMO
Constructing organic near-infrared (NIR) luminescent materials to confront the formidable barrier of "energy gap law" remains challenging. Herein, two NIR thermally activated delayed fluorescence (TADF) molecules named T-ß-IQD and TIQD were developed by connecting N,N-diphenylnaphthalen-2-amine and triphenylamine with a novel electron withdrawing unit 6-(4-(tert-butyl)phenyl)-6H-indolo[2,3-b]quinoxaline-2,3-dicarbonitrile. It is confirmed NIR-TADF emitters concurrent with aggregation-induced emission effect, J-aggregate with intra- and intermolecular CNâ â â H-C and C-Hâ â â π interactions, and large center-to-center distance in solid states can boost the emissive efficiencies both in thin films and non-doped organic light-emitting diodes (OLEDs). Consequently, the T-ß-IQD-based non-doped NIR-OLED achieved the maximum external quantum efficiency (EQEmax ) of 9.44 % with emission peak at 711â nm, which is one of the highest efficiencies reported to date for non-doped NIR-OLEDs.
RESUMO
Dinuclear Pt(III) complexes were commonly reported to have short-lived lowest-lying triplet states, resulting in extremely weak or no photoluminescence. To overcome this obstacle, a new series of dinuclear Pt(III) complexes, named Pt2a-Pt2c, were strategically designed and synthesized using donor (D)-acceptor (A)-type oxadiazole-thiol chelates as bridging ligands. These dinuclear Pt(III) complexes possess a d7-d7 electronic configuration and exhibit intense phosphorescence under ambient conditions. Among them, Pt2a exhibits orange phosphorescence maximized at 618 nm in degassed dichloromethane solution (Φp ≈ 8.2%, τp ≈ 0.10 µs) and near-infrared (NIR) emission at 749 nm (Φp ≈ 10.1% τp ≈ 0.66 µs) in the crystalline powder and at 704 nm (Φp ≈ 33.1%, τp ≈ 0.34 µs) in the spin-coated neat film. An emission blue-shifted by more than 3343 cm-1 is observed under mechanically ground crystalline Pt2a, affirming intermolecular interactions in the solid states. Time-dependent density functional theory (TD-DFT) discloses the lowest-lying electronic transition of Pt2a-Pt2c complexes to be a bridging ligand-metal-metal charge transfer (LMMCT) transition. The long-lived triplet states of these dinuclear platinum(III) complexes may find potential use in lighting. Employing Pt2a as an emitter, high-performance organic light-emitting diodes (OLEDs) were fabricated with NIR emission at 716 nm (η = 5.1%), red emission at 614 nm (η = 8.7%), and white-light emission (η = 11.6%) in nondoped, doped (in mCP), and hybrid (in CzACSF) devices, respectively.
RESUMO
Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate IrIII complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five IrIII complexes, Px-21-23, Cz-4, and Cz-5, have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand-metal-ligand bite angles of 166-170°, which are larger than the typical bite angle of 153-155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)3 ] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQEmax ) of 18.7 % and CIEx,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100â cd m-2 due to efficiency roll-off.
RESUMO
The progress of white organic light-emitting diodes (WOLEDs) via adopting fluorescent and phosphorescent organic materials have attracted commercial interest for their broad range of visible spectrum and potential of 100 % internal quantum efficiency. In this account, smart molecular designs for developing efficient phosphorescent host and good color purity blue fluorescent emitters are prepared to be discussed, especially donor-acceptor modification to regulate their triplet states and bipolar transport properties. Rational device configuration design strategies were also introduced by cooperating with efficient conventional fluorescent and thermally activated delayed fluorescent emitting molecules to achieve full exciton utilization and simplified device structures, further suggesting perspectives of potentially low-cost, ideal performance and promoted operational lifetime in WOLED devices.
RESUMO
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.
RESUMO
Thermally activated delayed fluorescent (TADF) materials generally suffer from severe concentration quenching. Efficient non-doped TADF emitters are generally highly twisted aromatic amine-based compounds with isolated chemical moieties. Herein we demonstrate that co-facial packing and strong π-π intermolecular interactions give rise to bright TADF emissions in non-doped film and crystalline states within the compound 2,4-diphenyl-6-(thianthren-1-yl)-1,3,5-triazine (oTE-DRZ). Quantum chemistry simulations indicate that a disperse outer orbital of sulfur atoms, a folded thianthrene plane (for a reduced donor-acceptor distance), and a triazine acceptor with n-π* character, generate a spatially conjugated transition with a small singlet-triplet splitting energy. In company with a highly emissive non-doped film, the corresponding organic light-emitting diode achieved a 20.6 % external quantum efficiency, verifying its potential for high-performance optoelectronic applications. In a crystalline state, it was verified that intra- and intermolecular dual TADF assisted by a hidden room-temperature phosphorescent state. This state could preserve the long-lived excitons while suppressing non-radiation, and it could serve as a "spring-board" for cascade up-conversion processes. The oTE-DRZ crystal showed greenish-blue emission with a very high photoluminescent quantum yield of approximately 87 %, which is the highest among all TADF crystals reported to date.