High-performance deep-blue electroluminescence from multi-resonance TADF emitters with a spirofluorene-fused double boron framework.

The development of multi-resonance thermally activated delayed fluorescence (MR-TADF) materials in the deep-blue region is highly desirable. A usual approach involves constructing an extended MR-TADF framework; however, it may also intensify aggregate-caused quenching issues and thereby reduce device efficiency. In this study, we develop a molecular design strategy that fuses the MR-TADF skeleton with 9,9'-spirobifluorene (SF) units to create advanced deep-blue emitters. The SF moiety facilitates high-yield one-shot bora-Friedel-Crafts reaction towards an extended skeleton and mitigates interchromophore interactions as a steric group. Our findings reveal that orbital interactions at the fusion site significantly influence the electronic structure, and optimizing the fusion mode allows for the development of emitters with extended conjugation length while maintaining non-bonding character. The proof-of-concept emitter exhibits narrowband emission in the deep-blue region, a near-unity photoluminescence quantum yield, and a fast k RISC of 2.4 × 105 s-1. These exceptional properties enable the corresponding sensitizer-free OLED to achieve a maximum external quantum efficiency (EQEmax) of 39.0% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.13, 0.09). Furthermore, the hyperfluorescence device realizes an EQEmax of 40.4% with very low efficiency roll-off.

Harmonization of rapid triplet up-conversion and singlet radiation enables efficient and stable white OLEDs.

White organic light-emitting diodes (WOLEDs) hold significant promise in illumination and displays, but achieving high efficiency while maintaining stability is an ongoing challenge. Here, we strategically combine a blue donor-acceptor thermally activated delayed fluorescence (TADF) emitter featuring rapid reverse intersystem crossing rate and a yellow multi-resonance TADF emitter renowned for the fast radiative transition process to achieve warm WOLEDs with exceptional power efficiency exceeding 190 lm W-1 and external quantum efficiency (EQE) of 39%, setting records for WOLEDs. Meanwhile, these devices also exhibit an extended operational lifetime (LT80) of 446 h at an initial luminance of 1000 cd m-2. Another group of blue and yellow emitters based on our strategy achieves a standard white emission and a high EQE of 35.6%, confirming the universality of our strategy. This work presents a versatile strategy to harmonize singlet exciton radiation and triplet exciton up-conversion, thus achieving a win-win situation of efficiency and stability.

Gold Coordination-Accelerated Multi-Resonance TADF Emission for Efficient Solution-Processible Ultrapure Deep-Blue OLEDs.

Multi-resonance (MR) type emitters have emerged as highly promising candidates for high-resolution organic light-emitting diodes (OLEDs). However, thermally activated delayed fluorescence (TADF) emissions with simultaneous short excited state lifetimes and ultrapure blue color (a CIEy close to 0.046 and an emission peak >440 nm) have rarely been obtained for MR emitters. Herein, we report a design of dual gold-coordinated MR molecules to achieve efficient and short-lived ultrapure blue TADF emission. The dinuclear Au(I) complex, namely iPrAuBN, shows a narrowband deep-blue emission with a peak maximum of 448 nm and a full width at half maximum (FWHM) of 29 nm in doped film. The coordination with two Au atoms significantly shortens the delayed fluorescence lifetime to 7.8 µs in comparison to 60.6 µs for the parental organic analogue. Solution-processed OLED doped with iPrAuBN demonstrates an ultrapure blue electroluminescence with a peak maximum of 442 nm, a FWHM of 19 nm, CIE coordinates of (0.154, 0.036), and a maximum external quantum efficiency of 14.8 %.

Nonplanar structure accelerates reverse intersystem crossing of TADF emitters: nearly 40% EQE and relieved efficiency roll off.

Exploring strategies to enhance reverse intersystem crossing (RISC) is of great significance to develop efficient thermally activated delayed fluorescent (TADF) molecules. In this study, we investigate the substantial impact of nonplanar structure on improving the rate of RISC (k RISC). Three emitters based on spiroacridine donors are developed to evaluate this hypothesis. All molecules exhibit high photoluminescent quantum yields (PLQYs) of 96-98% due to their rigid donor and acceptor. Leveraging the synergistic effects of heavy element effect and nonplanar geometry, S2-TRZ exhibits an accelerated k RISC of 24.2 × 105 s-1 compared to the 11.1 × 105 s-1 of S1-TRZ, which solely incorporates heavy atoms. Additionally, O1-TRZ possesses a further lower k RISC of 9.42 × 105 s-1 because of the absence of these effects. Remarkably, owing to the high PLQYs and suitable TADF behaviors, devices based on these emitters exhibit state-of-the-art performance, including a maximum external quantum efficiency of up to 40.1% and maximum current efficiency of 124.7 cd A-1. More importantly, devices utilizing S2-TRZ as an emitter achieve a relieved efficiency roll-off of only 7% under 1000 cd m-2, in contrast to the 12% for O1-TRZ and 11% for S1-TRZ, respectively. These findings advance our fundamental understanding of TADF processes for high-performance electroluminescent devices.

Multi-resonance thermally activated delayed fluorescence polymers for high-efficiency and narrowband solution-processed green OLEDs.

A series of green multi-resonance thermally activated delayed fluorescence polymeric emitters featuring conjugation-interrupted main chains were facilely prepared via metal-free superacid-catalyzed Friedel-Crafts polyhydroxyalkylation. These emitters exhibited photoluminescence quantum yields of up to 76% and small full-widths at half maximum of 35-38 nm in toluene. The corresponding solution-processed OLEDs achieved an excellent maximum external quantum efficiency of 19.4%, with CIE coordinates of (0.20, 0.62).

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).

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.

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.

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.

Deep-Blue Narrowband Hetero[6]helicenes Showing Circularly Polarized Thermally Activated Delayed Fluorescence Toward High-Performance OLEDs.

Helicenes exhibit substantial potential as circularly polarized luminescence (CPL) active molecules. However, their application in circularly polarized organic light-emitting diodes (CP-OLEDs) is typically hindered by the challenge of integrating both high color purity and efficient triplet-harvesting capability, particularly in the blue spectral region. Herein, a series of hetero[6]helicene-based emitters that is strategically engineered through the helical extension of a deep-blue double-boron-based multiple resonance thermally activated delayed fluorescence (MR-TADF) motif, is introduced. Importantly, the helical extension does not cause apparent structural deformation or perturb frontier molecular orbitals; thus, preserving the deep-blue emission and MR-TADF characteristics of the parent molecule. This approach also leads to reduced reorganization energy, resulting in emitters with narrower linewidth and higher photoluminescence quantum yield. Further, the helical motif enhances the racemization barrier and leads to improved CPL performance with luminescence dissymmetry factor values up to 1.5 × 10-3 . Exploiting these merits, devices incorporating the chiral dopants demonstrate deep-blue emission within the Broadcast Service Television 2020 color-gamut range, record external quantum efficiencies (EQEs) up to 29.3%, and have distinctive circularly polarized electroluminescence (CPEL) signals. Overall, the authors' findings underscore the helical extension as a promising strategy for designing narrowband chiroptical materials and advancing high-definition displays.

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.

Simultaneously enhancing the planarity and electron-donating capability of donors for through-space charge transfer TADF towards deep-red emission.

Through-space charge transfer (TSCT) has been proven effective for designing thermally activated delayed fluorescence (TADF) emitters due to the separation of the frontier molecular orbitals. Although tuning of the interaction between the donor and acceptor by controlling the conformation is known to be crucial for the photophysical properties of TSCT excited states, it remains a challenge to realize efficient red and deep-red emissions. Herein, we designed two TSCT molecules, namely TPXZ-QX and TPXZ-2QX, by using oxygen-bridged triphenylamine (TPXZ) as the electron donor with enhanced planarity and electron-donating capability. With a face-to-face orientation of the donor and acceptor segments and close π-π contacts, the new emitters have strong intramolecular noncovalent donor-acceptor interactions. The emissions of TPXZ-QX and TPXZ-2QX in doped thin films lie in the red (λmax = 632 nm) to deep-red (λmax = 665 nm) region. The photoluminescence quantum yields are 41% and 32% for TPXZ-QX and TPXZ-2QX, respectively. Organic light-emitting diodes (OLEDs) based on TPXZ-QX and TPXZ-2QX show external quantum efficiencies (EQEs) of up to 13.8% and 11.4%, respectively. This work indicates that the modulation of TSCT excited states based on strong intramolecular cofacial π-stacking interactions is a viable choice for the development of high-efficiency long-wavelength TADF 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.

Precise modulation of multiple resonance emitters toward efficient electroluminescence with pure-red gamut for high-definition displays.

Multiple resonance (MR) compounds have garnered substantial attention for their prospective utility in wide color gamut displays. Nevertheless, developing red MR emitters with both high efficiency and saturated emission color remains demanding. We herein introduce a comprehensive strategy for spectral tuning in the red region by simultaneously regulating the π-conjugation and electron-donating strengths of a double boron-embedded MR skeleton while preserving narrowband characteristics. The proof-of-concept materials manifested emissions from orange-red to deep red, with bandwidths below 0.12 eV. The pure-red device based on CzIDBNO displayed superior color purity with CIE coordinates of (0.701, 0.298), approaching the Broadcast Television 2020 standard. In concert with high photoluminescence quantum yield and strong horizontal dipole orientation, CzIDBNO also achieved a maximum external quantum efficiency of 32.5% and a current efficiency of 20.2 cd A-1, outstripping prior reported organic light-emitting diodes (OLEDs) with CIEx exceeding 0.68. These findings offer a roadmap for designing high-performance emitters with exceptional color purity for future OLED material research advancements.

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.

Multi-spiro junctions enable efficient thermally activated delayed fluorescent emitter.

A new acridine donor with trispiro junctions is developed for assembling a highly efficient thermally activated delayed fluorescence emitter. The multispiro junctions ensure a rigid geometry that leads to a well-suppressed nonradiative decay. The resulting electroluminescent devices achieve a high external quantum efficiency of 34.2%.

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.

Discrete Mononuclear Platinum(II) Complexes Realize High-Performance Red Phosphorescent OLEDs with EQEs of up to 31.8% and Superb Device Stability.

Designing mononuclear platinum(II) complexes that do not rely on intermolecular aggregation for high-performance red organic light-emitting diodes remains a formidable challenge. In this work, three robust red-emitting Pt(II) complexes are created by utilizing a rigid 4-coordination configuration, where the ligands are formed by linking electron-donor of triphenylamine (TPA) moieties with electron-acceptor of pyridine, isoquinoline, and/or δ-carboline units. The thermal stability, electrochemical, and photophysical properties of the complexes are thoroughly examined. The complexes display efficient red phosphorescence, with high photoluminescence quantum yields and short excited lifetimes. The OLEDs dope with these complexes exhibit high maximum external quantum efficiencies (EQEs) of up to 31.8% with minimal efficiency roll-off even at high brightness. Significantly, the devices demonstrate exceptional long operational lifetime, with a T90 lifetime of over 14000 h at initial luminance of 1000 cd m-2 , indicating the potential for these complexes to be practically utilizes.

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.

Dynamic bond interactions fine-tune the properties of multiple resonance emitters towards highly efficient narrowband green OLEDs.

Multiple resonance (MR) molecules based on a B/N polycyclic aromatic framework are the cutting-edge materials in the field of organic light-emitting diodes (OLEDs) owing to their superb photophysical properties. Tailoring the MR molecular framework with various functional groups toward ideal properties has become an emerging topic in the field of materials chemistry. Dynamic bond interactions are versatile and powerful tools in regulating the properties of materials. Herein, the pyridine moiety, which presents high affinity to form dynamic bond interactions such as hydrogen bonds and N→B dative bonds, was introduced into the MR framework for the first time, and the designed emitters are synthesized in a feasible way. The introduction of the pyridine moiety not only maintained the conventional MR properties of the emitters, but also endowed the emitters with tunable emission spectra, narrowed emission, enhanced photoluminescence quantum yield (PLQY), and intriguing supramolecular assembly in the solid state. Thanks to the overall superior properties brought by the hydrogen-bond promoted molecular rigidity, green OLEDs based on the emitter exhibit excellent device performance with external quantum efficiency (EQE) up to 38% and a small FWHM of 26 nm, together with good roll-off performance.