Orienting Group Directed Cascade Borylation for Efficient One-Shot Synthesis of 1,4-BN-Doped Polycyclic Aromatic Hydrocarbons as Narrowband Organic Emitters.

1,4-BN-doped polycyclic aromatic hydrocarbons (PAHs) have emerged as very promising emitters in organic light-emitting diodes (OLEDs) due to their narrowband emission spectra that may find application in high-definition displays. While considerable research has focused on investigating the properties of these materials, less attention has been placed on their synthetic methodology. Here we developed an efficient synthetic method for 1,4-BN-doped PAHs, which enables sustainable production of narrowband organic emitting materials. By strategically introducing substituents, such as methyl, tert-butyl, phenyl, and chloride, at the C5 position of the 1,3-benzenediamine substrates, we achieved remarkable regioselective borylation in the para-position of the substituted moiety. This approach facilitated the synthesis of a diverse range of 1,4-BN-doped PAHs emitters with good yields and exceptional regioselectivity. The synthetic method demonstrated excellent scalability for large-scale production and enabled late-stage transformation of the borylated products. Mechanistic investigations provided valuable insights into the pivotal roles of electron effect and steric hindrance effect in achieving highly efficient regioselective borylation. Moreover, the outstanding device performance of the synthesized compounds 10 b and 6 z, underscores the practicality and significance of the developed method.

Narrowband Near-Infrared Multiple-Resonance Thermally Activated Delayed Fluorescence Emitters towards High-Performance and Stable Organic Light-Emitting Diodes.

Multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials are highly coveted for their high efficiency and narrowband emission in organic light-emitting diodes (OLEDs). Nevertheless, the development of near-infrared (NIR) MR-TADF emitters remains a formidable challenge. In this study, we design two new NIR MR-TADF emitters, PXZ-R-BN and BCz-R-BN, by embedding 10H-phenoxazine (PXZ) and 7H-dibenzo[c,g]carbazole (BCz) fragments to increase the electron-donating ability or extending π-conjugation on the framework of para-boron fusing polycyclic aromatic hydrocarbons (PAHs). Both compounds emit in the NIR region, with a full-width at half-maximum (FWHM) of 49 nm (0.13 eV) for PXZ-R-BN and 43 nm (0.11 eV) for BCz-R-BN in toluene. To sensitize the two NIR MR-TADF emitters in OLEDs, a new platinum complex, Pt-1, is designed as a sensitizer. The PXZ-R-BN-based sensitized OLEDs achieve a maximum external quantum efficiency (EQEmax ) of nearly 30 % with an emission band at 693 nm, and exceptional long operational stability with an LT97 (time to 97 % of the initial luminance) value of 39084 h at an initial radiance of 1000 mW sr-1 m-2 . The BCz-R-BN-based OLEDs reach EQEmax values of 24.2 % with an emission band at 713 nm, which sets a record value for NIR OLEDs with emission bands beyond 700 nm.

Charge Transfer Excited State Promoted Multiple Resonance Delayed Fluorescence Emitter for High-Performance Narrowband Electroluminescence.

Multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters are promising candidates for narrowband organic light-emitting diodes, but their electroluminescent performance is typically hindered by the slow reverse intersystem crossing rate (kRISC). Herein, we present an effective strategy to introduce a multichannel reverse intersystem crossing (RISC) pathway with large spin-orbit coupling by orthogonally linking an electron-donating unit to the MR framework. Through delicate manipulation of the excited-state energy levels, an additional intersegmental charge transfer triplet state could be "silently" induced without perturbing the MR character of the lowest excited singlet state. The proof-of-concept emitter CzBN3 not only affords 23-fold increase of kRISC compared with its prototypical MR skeleton but also realizes close-to-unity photoluminescence quantum yield, large radiative rate constant, and very narrow emission spectrum. These merits enable high maximum external quantum efficiency (EQEmax) of up to 37.1% and alleviated efficiency roll-off in the sensitizer-free device (EQE1000 = 30.4%), and a further boost of efficiency (EQEmax/1000 = 42.3/34.1%) is realized in the hyperfluorescent device. The state-of-the-art electroluminescent performance validates the superiority of our molecular design strategy.

Naphthalene-Embedded Multi-Resonance Emitters Enabling Efficient Narrow Emissive Blue OLEDs.

Great achievements have been made in the development of organic light-emitting diodes in recent decades. However, achieving high color purity for blue emitters remains a challenge. In this study, we have designed and synthesized three naphthalene (NA)-embedded multi-resonance (MR) emitters, named SNA, SNB and SNB1, based on N-B-O frameworks with isomer variations for finely adjusting the photophysical properties. These emitters show tunable blue emission with emission peaks of 450-470 nm. Small full width of half maximum (FWHM) of 25-29 nm are achieved in these emitters, indicating the well maintaining of molecular rigidity and MR effect with NA extension. Such design also ensures a fast radiative decay. However, no obvious delayed fluorescence is observed in all three emitters due to the relatively large energy differences between the first singlet and triplet excited states. Both SNA and SNB enable high electroluminescent (EL) performance in doped devices with external quantum efficiency (EQE) of 7.2 and 7.9 %, respectively. When applying the sensitized strategy, devices based on SNA and SNB show huge improvement with EQE of 29.3 and 29.1 %. More importantly, SNB with twist geometry enables stable EL spectra with almost unchanged FWHM under different doping concentrations. This work demonstrates the potential of NA extension design in constructing narrowband emissive blue emitters.

Narrowband Fluorescent Emitters Based on BN-Doped Polycyclic Aromatic Hydrocarbons for Efficient and Stable Organic Light-Emitting Diodes.

Organic light-emitting diodes (OLEDs) using conventional fluorescent emitters are currently attracting considerable interests due to outstanding stability and abundant raw materials. To construct high-performance narrowband fluorophores to satisfy requirements of ultra-high-definition displays, a strategy fusing multi-resonance BN-doped moieties to naphthalene is proposed to construct two novel narrowband fluorophores. Green Na-sBN and red Na-dBN, manifest narrow full-width at half-maxima of 31 nm, near-unity photoluminescence quantum yields and molecular horizontal dipole ratios above 90 %. Their OLEDs exhibit the state-of-the-art performances including high external quantum efficiencies (EQE), ultra-low efficiency roll-off and long operational lifetimes. The Na-sBN-based device achieves EQE as high as 28.8 % and remains 19.8 % even at luminance of 100,000 cd m-2 , and Na-dBN-based device acquires a record-high EQE of 25.2 % among all red OLEDs using pure fluorescent emitters.

A Tetrahedral Bisacridine Donor Enables Fast Radiative Decay in Thermally Activated Delayed Fluorescence Emitter.

Achieving high efficiency and low efficiency roll-off simultaneously is of great significance for further application of thermally activated delayed fluorescent (TADF) emitters. A balance between radiative decay and reversed intersystem crossing must be carefully established. Herein, we propose a qunolino-acridine (QAc) donor composing two acridine with both planar (pAc) and bended (bAc) geometries. Combining with triazine, a TADF emitter QAc-TRZ is assembled. The pAc provides a well interaction with triazine which ensures a decent TADF behavior, while the bAc offers a delocalization of highest occupied molecular orbital (HOMO) which guarantees an enhancement of radiative decay. Remarkably, QAc-TRZ enables a highly efficient organic light emitting diode (OLED) with maximum external quantum efficiency (EQE) of 37.3 %. More importantly, the efficiencies under 100/1000 cd m-2 stay 36.3 % and 31.7 %, respectively, and remain 21.5 % even under 10 000 cd m-2 .

Peripherally Heavy-Atom-Decorated Strategy Towards High-Performance Pure Green Electroluminescence with External Quantum Efficiency over 40 .

Heavy-atom integration into thermally activated delayed fluorescence (TADF) molecule could significantly promote the reverse intersystem crossing (RISC) process. However, simultaneously achieving high efficiency, small roll-off, narrowband emission and good operational lifetime remains a big challenge for the corresponding organic light-emitting diodes (OLEDs). Herein, we report a pure green multi-resonance TADF molecule BN-STO by introducing a peripheral heavy atom selenium onto the parent BN-Cz molecule. The organic light-emitting diode device based on BN-STO exhibited state-of-the-art performance with a maximum external quantum efficiency (EQE) of 40.1 %, power efficiency (PE) of 176.9 lm W-1 , well-suppressed efficiency roll-off and pure green gamut. This work reveals a feasible strategy to reach a balance between fast RISC process and narrow full width at half maximum (FWHM) of MR-TADF by heavy atom effect.

Manipulating Exciton Dynamics toward Simultaneous High-Efficiency Narrowband Electroluminescence and Photon Upconversion by a Selenium-Incorporated Multiresonance Delayed Fluorescence Emitter.

Multiresonance thermal activated delayed fluorescence (MR-TADF) materials with an efficient spin-flip transition between singlet and triplet excited states remain demanding. Herein, we report an MR-TADF compound (BN-Se) simultaneously possessing efficient (reverse) intersystem crossing (ISC/RISC), fast radiative decay, close-to-unity quantum yield, and narrowband emission by embedding a single selenium atom into a common 4,4'-diazaborin framework. Benefitting from the high RISC efficiency accelerated by the heavy-atom effect, organic light-emitting diodes (OLEDs) based on BN-Se manifest excellent performance with an external quantum efficiency of up to 32.6% and an ultralow efficiency roll-off of 1.3% at 1000 cd m-2. Furthermore, the high ISC efficiency and small inherent energy loss also render BN-Se a superior photosensitizer to realize the first example of visible (λex > 450 nm)-to-UV (λem < 350 nm) triplet-triplet annihilation upconversion, with a high efficiency (21.4%) and an extremely low threshold intensity (1.3 mW cm-2). This work not only aids in designing advanced pure organic molecules with fast exciton dynamics but also highlights the value of MR-TADF compounds beyond OLED applications.

Rigid Bridge-Confined Double-Decker Platinum(II) Complexes Towards High-Performance Red and Near-Infrared Electroluminescence.

A molecular design to high-performance red and near-infrared (NIR) organic light-emitting diodes (OLEDs) emitters remains demanding. Herein a series of dinuclear platinum(II) complexes featuring strong intramolecular Pt⋅⋅⋅Pt and π-π interactions has been developed by using N-deprotonated α-carboline as a bridging ligand. The complexes in doped thin films exhibit efficient red to NIR emission from short-lived (τ=0.9-2.1 µs) triplet metal-metal-to-ligand charge transfer (3 MMLCT) excited states. Red OLEDs demonstrate high maximum external quantum efficiencies (EQEs) of up to 23.3 % among the best PtII -complex-doped devices. The maximum EQE of 15.0 % and radiance of 285 W sr-1 m-2 for NIR OLEDs (λEL =725 nm) are unprecedented for devices based on discrete molecular emitters. Both red and NIR devices show very small efficiency roll-off at high brightness. Appealing operational lifetimes have also been revealed for the devices. This work sheds light on the potential of intramolecular metallophilicity for long-wavelength molecular emitters and electroluminescence.

Narrowband Emissive TADF Conjugated Polymers towards Highly Efficient Solution-Processible OLEDs.

Thermally activated delayed fluorescence (TADF) conjugated polymers usually show broad emission spectra due to the large structure relaxation, which is not desirable for high-quality organic light-emitting diode (OLED) displays. Herein, through attaching multiple resonance (MR) induced emitting moiety as pendant onto the polycarbazole backbone, TADF conjugated polymers with narrowband emission are demonstrated. The obtained conjugated polymers exhibit typical TADF characteristics with narrowband emission with full-width at half-maximums (FWHMs) of 33-43 nm. The solution-processed devices employing these polymers as emissive layers realize excellent performances with maximum external quantum efficiency (EQE) of 17.5 %, emission peak at 496 nm and FWHM of 34 nm.

Chiral Multi-Resonance TADF Emitters Exhibiting Narrowband Circularly Polarized Electroluminescence with an EQE of 37.2 .

Highly efficient circularly polarized luminescence (CPL) emitters with narrowband emission remain a formidable challenge for circularly polarized OLEDs (CP-OLEDs). Here, a promising strategy for developing chiral emitters concurrently featuring multi-resonance thermally activated delayed fluorescence (MR-TADF) and circularly polarized electroluminescence (CPEL) is demonstrated by the integration of molecular rigidity, central chirality and MR effect. A pair of chiral green emitters denoted as (R)-BN-MeIAc and (S)-BN-MeIAc is designed. Benefited by the rigid and quasi-planar MR-framework, the enantiomers not only display mirror-image CPL spectra, but also exhibit TADF properties with a high photoluminescence quantum yield of 96 %, a narrow FWHM of 30 nm, and a high horizontal dipole orientation of 90 % in the doped film. Consequently, the enantiomer-based CP-OLEDs achieved excellent external quantum efficiencies of 37.2 % with very low efficiency roll-off, representing the highest device efficiency of all the reported CP-OLEDs.

Au⋠⋠⋠H-C Interactions Support a Robust Thermally Activated Delayed Fluorescence (TADF) Gold(I) Complex for OLEDs with Little Efficiency Roll-Off and Good Stability.

The practical use of luminescent mononuclear gold(I) complexes as optoelectronic materials has been limited by their inferior stability. Herein we demonstrate a strategy to improve the stability of gold(I) complexes which display thermally activated delayed fluorescence (TADF). A highly rigid and groove-like σ-donating aryl ligand has been used to form dual Au⋅⋅⋅H-C hydrogen bonds. The secondary metal-ligand interactions have been authenticated by single-crystal structure, NMR spectroscopy and theoretical simulations. The TADF AuI complex exhibits appealing emission properties (photoluminescence quantum yield=76 %; delayed fluorescence lifetime=1.2 µs) and much improved thermal and photo-stability. Vacuum-deposited organic light-emitting diodes (OLEDs) show promising electroluminescence with a maximum external quantum efficiency (EQE) over 23 % and negligible efficiency roll-off even at 10 000 cd m-2 . An estimated LT50 longer than 77 000 h with initial luminance of 100 cd m-2 reveals good operational stability. This work suggests a way for design of stable luminescent gold(I) complexes.

Extending the π-Skeleton of Multi-Resonance TADF Materials towards High-Efficiency Narrowband Deep-Blue Emission.

Multi-resonance TADF (MR-TADF) emitters are promising for high-resolution OLEDs, but the concurrent optimization of excited-state dynamics and color purity remains a tough challenge. Herein, three deep-blue MR-TADF compounds (BN1-BN3) featuring gradually enlarged ring-fused structures and increased rigidity are accessed by lithium-free borylation in high yields from the same precursor, with all the emitters possessing CIEy coordinates below 0.08. Structure-property investigations demonstrate a strategic improvement of the oscillator strength (fosc ) and acceleration of the reverse intersystem crossing (RISC) process by extending the π-skeleton, where BN3 realizes a maximum external quantum efficiency (EQE) of 37.6 % and reduced roll-off, thus showing the best efficiency reported for deep-blue TADF OLEDs. The internal regulation of the efficiency and color purity of these compounds validate the general effectiveness to achieve advanced deep-blue narrowband emitters with higher-order boron/nitrogen-based MR motifs.

High Performance Near-Infrared Emitters with Methylated Triphenylamine and Thiadiazolo[3,4-g]quinoxaline-Based Fluorophores.

Three near-infrared emitters (2TPA-QBT, 2MeTPA-BT and TPA-QBT-MeTPA) were rationally designed and synthesized. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations showed that the introduction of mono- or di-methyl groups between the donors and acceptor could result in the spatial configuration changing greatly for 2MeTPA-QBT and TPA-QBT-MeTPA compared to their parent compound 2TPA-QBT. The emission of TPA-QBT-MeTPA had a more obvious hybridized local and charge transfer feature (HLCT) based on the influence of the steric hindrance of the methyl substituent. Attributed to their different spatial configurations and luminescence mechanisms, different emission wavelengths with photoluminescent quantum yields of 26%, 38% and 34% in toluene, as well as 24%, 27% and 31% in 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) doped film, were observed for 2TPA-QBT, 2MeTPA-QBT and TPA-QBT-MeTPA, respectively. The constructed organic light-emitting devices (OLEDs) displayed electroluminescence with emission peaks at 728, 693 and 710 nm, with maximum external quantum efficiencies of 1.58%, 1.33% and 3.02% for the 2TPA-QBT, 2MeTPA-QBT and TPA-QBT-MeTPA-doped OLEDs, respectively. This work illustrated the effect of spatial configuration changes on the luminescence properties of donor-acceptor-type organic emitters.

Vacuum-Drying Processed Micrometer-Thick Stable CsPbBr3 Perovskite Films with Efficient Blue-To-Green Photoconversion.

Metal halide perovskite materials have attracted great attention owing to their fascinating optoelectronic characteristics and low cost fabrication via facile solution processing. One of the potential applications of these materials is to employ them as color-conversion layers (CCLs) for visible blue light to achieve full-color displays. However, obtaining thick perovskite films to realize complete color conversion is a key challenge. Here, the fabrication of micrometer-level thick CsPbBr3 perovskite films is presented through a facile vacuum drying approach. An efficient green photoconversion is realized in a 3.8 µm thick film from blue light @ 463 nm. For a back luminance of 1000 cd m-2 , the brightness of the resulting green emission can reach as high as 200 cd m-2 . Furthermore, only ≈2% of decay in brightness is observed when the films are tested after 18 days of exposure to ambient environment. In addition, a potential design is also proposed for full-color displays with perovskite materials incorporated as CCLs.

Star-Shaped Macromolecules with the Core of Hexakis-(fluoren-2-yl)benzene and the Periphery of Pyridine: Synthesis and Application as Solution-Processable Electron-Transport Materials.

Three new star-shaped macromolecules with hexakis(fluoren-2-yl)benzene as the core and pyridine as the periphery (2Py-HFB, 3Py-HFB, and 4Py-HFB) are synthesized and characterized. The synthetic conditions of octacarbonyldicobat-catalyzed cycloaddition reaction for different alkyne precursors are investigated. The coordination interaction between the pyridine ring of alkyne precursor and the cobalt catalyst may result in very low yield of the cyclotrimerization product. However, with the increase of the catalyst loading, the yields of the intermediates of cyclopentadienone are enhanced. Then, the desired cyclotrimerization products can be obtained by the Diels-Alder reactions of cyclopentadienone with acetylene in good yield. These new compounds exhibit good thermal stability and favorable electron affinity. By using the new compounds as electron-transporting materials, all-solution-processed phosphorescent organic light-emitting devices (OLEDs) show good performance with a maximum current efficiency of 5.6 cd A(-1) and maximum external quantum efficiency of 4.68%.

Efficient solution-processed double-layer red OLEDs based on a new europium complex with a carbazole group.

A new europium complex EuL3 (Phen) was used as guest dopant, and a blend of Polyvinylcarbazole and 2-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PVK and PBD) as host matrix. Efficient red organic light-emitting devices (OLEDs) with double-layer structures were manufactured via a solution-processed technique. The guest-doped levels were 1, 3 and 5 wt% relative to the blend mass, respectively. For the 1 wt% doping-level device, the luminous efficiency and luminance were up to 2.96 cd/A and 635.78 cd/m(2) with emissions from both EuL3 (Phen) and from the host; for the 3 wt% doping-level device, the maximum luminous efficiency and luminance were 1.01 cd/A and 370.91 cd/m(2) for the single emission from EuL3 (Phen) only.

A diphenylphosphine oxide decorated multi-resonance TADF emitter for narrowband green electroluminescence with an EQE of 32.4.

A new narrowband thermally activated delayed fluorescence emitter, PhCzBN-PO, was developed by incorporating the diphenylphosphine oxide (DPPO) group into a multi-resonance core. The unique properties of DPPO enabled PhCzBN-PO to achieve pure green emission and a nonplanar structure. The resulting electroluminescent devices achieved high external quantum efficiencies up to 32.4% with extremely low efficiency roll-off and pure-green emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.24, 0.67).

Integration of fine-tuned chiral donor with hybrid long/short-range charge-transfer for high-performance circularly polarized electroluminescence.

The synergistic integration of a fine-tuned chiral donor with a hybrid long/short-range charge-transfer mechanism offers an accessible pathway to construct highly efficient circularly polarized emitters. Consequently, a notable dissymmetry factor of 1.6 × 10-3, concomitantly with a record-setting maximum external quantum efficiency of 37.4%, is synchronously realized within a single embodiment.

B‒N covalent bond-involved π-extension of multiple resonance emitters enables high-performance narrowband electroluminescence.

Multi-boron-embedded multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters show promise for achieving both high color-purity emission and high exciton utilization efficiency. However, their development is often impeded by a limited synthetic scope and excessive molecular weights, which challenge material acquisition and organic light-emitting diode (OLED) fabrication by vacuum deposition. Herein, we put forward a B‒N covalent bond-involved π-extension strategy via post-functionalization of MR frameworks, leading to the generation of high-order B/N-based motifs. The structurally and electronically extended π-system not only enhances molecular rigidity to narrow emission linewidth but also promotes reverse intersystem crossing to mitigate efficiency roll-off. As illustrated examples, ultra-narrowband sky-blue emitters (full-width at half-maximum as small as 8 nm in n-hexane) have been developed with multi-dimensional improvement in photophysical properties compared to their precursor emitters, which enables narrowband OLEDs with external quantum efficiencies (EQEmax) of up to 42.6%, in company with alleviated efficiency decline at high brightness, representing the best efficiency reported for single-host OLEDs. The success of these emitters highlights the effectiveness of our molecular design strategy for advanced MR-TADF emitters and confirms their extensive potential in high-performance optoelectronic devices.