Efficient Blue Photo- and Electroluminescence from CF3-Decorated Cu(I) Complexes.

Luminescent organometallic complexes of earth-abundant copper(I) have long been studied in organic light-emitting diodes (OLED). Particularly, Cu(I)-based carbene-metal-amide (CMA) complexes have recently emerged as promising organometallic emitters. However, blue-emitting Cu(I) CMA complexes have been rarely reported. Here we constructed two blue-emitting Cu(I) CMA emitters, MAC*-Cu-CF3Cz and MAC*-Cu-2CF3Cz, by introducing one or two CF3 substitutes into carbazole ligands. Both complexes exhibited high thermal stability and blue emission colors. Moreover, two complexes exhibited different emission origins rooting from different donor ligands: a distinct thermally activated delayed fluorescence (TADF) from ligand-to-ligand charge transfer excited states for MAC*-Cu-CF3Cz or a dominant phosphorescence nature from local triplet excited state of the carbazole ligand for MAC*-Cu-2CF3Cz. Inspiringly, MAC*-Cu-CF3Cz had high photoluminescence quantum yields of up to 94 % and short emission lifetimes of down to 1.2 µs in doped films, accompanied by relatively high radiative rates in the 105 s-1 order. The resultant vacuum-deposited OLEDs based on MAC*-Cu-CF3Cz delivered pure-blue electroluminescence at 462 nm together with a high external quantum efficiency of 13.0 %.

Inkjet Printing of High-Color-Purity Blue Organic Light-Emitting Diodes with Host-Free Inks.

Inkjet printing technology offers a unique approach to producing direct-patterned pixels without fine metal masks for active matrix displays. Organic light-emitting diodes (OLEDs) consisting of thermally activated delayed fluorescence (TADF) emitters facilitate efficient light emission without heavy metals, such as platinum and iridium. Multi-resonance TADF molecules, characterized by their small full width at half maxima (FWHM), are highly suitable for the requirements of wide color-gamut displays. Herein, host-free TADF inks with a low concentration of 1 mg/mL were developed and inkjet-printed onto a seeding layer, concurrently serving as the hole-transporting layer. Attributed to the proof-of-concept of host-free inks printed on a mixed seeding layer, a maximum external quantum efficiency of 13.1% (improved by a factor of 21.8) was achieved in the inkjet-printed OLED, with a remarkably narrow FWHM of only 32 nm. Highly efficient energy transfer was facilitated by the effective dispersion of the sensitizer around the terminal emitters.

Through-Space Charge-Transfer Organogold(III) Complexes Enable High-Performance X-ray Scintillation and Imaging.

Organic scintillators have recently attracted growing attention for X-ray detection in industrial and medical applications. However, these materials still face critical obstacles of low attenuation efficiency and/or inefficient triplet exciton utilization. Here we developed a new category of organogold(III) complexes, Tp-Au-1 and Tp-Au-2, through adopting a through-space interaction motif to realize high X-ray attenuation efficiency and efficient harvesting of triplet excitons for emission. Thanks to the efficient through-space charge transfer process, this panel of complexes achieved higher photoluminescence quantum yield and shorter radiative lifetimes compared with the through-bond reference complexes. Inspiringly, these organogold(III) complexes exhibited polarity-dependent emission origins: thermally activated delayed fluorescence and/or phosphorescence. Under X-ray irradiation, Tp-Au-2 manifested intense radioluminescence together with a record-high scintillation light yield of 77,600 photons MeV-1 for organic scintillators. The resulting scintillator screens demonstrated high-quality X-ray imaging with >16.0 line pairs mm-1 spatial resolution, outstripping most organic and inorganic scintillators. This finding provides a feasible strategy for the design of superior organic X-ray scintillators.

Dynamic Reversible Full-Color Piezochromic Fluorogens Featuring Through-Space Charge-Transfer Thermally Activated Delayed Fluorescence and their Application as X-Ray Imaging Scintillators.

Thermally activated delayed fluorescence (TADF) emitters featuring through-space charge transfer (TSCT) can be excellent candidates for piezochromic luminescent (PCL) materials due to their structural dynamics. Spatial donor-acceptor (D-A) stacking arrangements enable the modulation of inter- and intramolecular D-A interactions, as well as spatial charge transfer states, under varying pressure conditions. Herein, we demonstrate an effective approach toward dynamic reversible full-color PCL materials with TSCT-TADF characteristics. Their single crystals exhibit a full-color-gamut PCL process spanning a range of 170 nm. Moreover, the TSCT-TADF-PCL emitters display a unity photoluminescence quantum yield, and show promising application in X-ray scintillator imaging.

A Rising Star: Luminescent Carbene-Metal-Amide Complexes.

Coinage metal (gold, silver, and copper) complexes are attractive candidates to substitute the widely studied noble metal complexes, such as, iridium(III) and platinum(II), as luminescent materials in organic light-emitting diodes (OLEDs). However, the development of coinage metal complexes exhibiting high emission quantum yields and short exciton lifetimes is still a formidable challenge. In the past few years, coinage metal complexes featuring a carbene-metal-amide (CMA) motif have emerged as a new class of luminescent materials in OLEDs. Thanks to the coinage metal-bridged linear geometry, coplanar conformation, and the formation of excited states with dominant ligand-to-ligand charge transfer character and reduced metal d-orbital participation, most CMA complexes have high radiative rates via thermally activated delayed fluorescence. Currently, the family of CMA complexes have rapidly evolved and remarkable progresses in CMA-based OLEDs have been made. Here, a Concept article on CMA complexes is presented, with a focus on molecular design principles, the correlation between molecular structure/conformation and optoelectronic properties, as well as OLED performance. The future prospects of CMA complexes are also discussed.

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.

Aggregation-Dependent Circularly Polarized Luminescence and Thermally Activated Delayed Fluorescence from Chiral Carbene-CuI -Amide Enantiomers.

The field of luminescent carbene-metal-amide (CMA) complexes and chiroptical-active materials has been blossoming in recent years, although chiroptical-active CMA complexes have not been reported so far. For the first time, a pair of chiral CuI -based CMA enantiomers, (R,R)-PSIPr*-Cu-DMAC and (S,S)-PSIPr*-Cu-DMAC, have been developed by using chiral phenyl-substituted N-heterocyclic carbenes as acceptor ligands in the CMA motif. The CuI -based CMA enantiomers exhibited aggregation-induced circularly polarized luminescence with a large luminescence dissymmetry factor of up to +0.027, the first reported for CMA complexes. This success originates from the limited ligand-ligand rotation freedom and asymmetrical packing pattern (helical structure) of the CMA enantiomers in the crystals. Moreover, these CuI enantiomers displayed inspiring aggregation-dependent thermally activated delayed fluorescence properties. These findings bring new insights into the optical properties of chiral CMA complexes from the perspective of aggregation states.

Achieving 37.1% Green Electroluminescent Efficiency and 0.09 eV Full Width at Half Maximum Based on a Ternary Boron-Oxygen-Nitrogen Embedded Polycyclic Aromatic System.

Herein, a ternary boron-oxygen-nitrogen embedded polycyclic aromatic hydrocarbon with multiple resonance thermally activated delayed fluorescence (MR-TADF), namely DBNO, is developed by adopting the para boron-π-boron and para oxygen-π-oxygen strategy. The designed molecule presents a vivid green emission with a high photoluminescence quantum yield (96 %) and an extremely narrow full width at half maximum (FWHM) of 19 nm/0.09 eV, which surpasses all previously reported green TADF emitters to date. In addition, the long molecular structure along the transition dipole moment direction endows it with a high horizontal emitting dipole ratio of 96 %. The organic light-emitting diode (OLED) based on DBNO reveals a narrowband green emission with a peak at 504 nm and a FWHM of 24 nm/0.12 eV. Particularly, a significantly improved device performance is achieved by the TADF-sensitization (hyperfluorescence) mechanism, presenting a FWHM of 27 nm and a maximum external quantum efficiency (EQE) of 37.1 %.

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.

Efficient Red Thermally Activated Delayed Fluorescence Emitters Based on a Dibenzonitrile-Substituted Dipyrido[3,2-a:2',3'-c]phenazine Acceptor.

How to construct efficient red-emitting thermally activated delayed fluorescence (TADF) materials is a challenging task in the field of organic light-emitting diodes (OLEDs). Herein, an electron acceptor moiety, 3,6-DCNB-DPPZ, with high rigidity and strong acceptor strength was designed by introducing two cyanobenzene groups into the 3,6-positions of a dipyrido[3,2-a:2',3'-c]phenazine unit. A red-emitting compound, 3,6_R, has been designed and synthesized by combining the rigid acceptor unit with two triphenylamine donors. Due to high molecular rigidity and strong intramolecular charge transfer characteristic in donor-acceptor-donor skeleton, 3,6_R exhibited a red emission with a high photoluminescence quantum yield of 86% and distinct TADF nature with short delayed fluorescence lifetime of about 1 microsecond. Accordingly, the OLED using 3,6_R as the guest emitter gained a high external quantum efficiency of 12.0% in the red region with an electroluminescence peak of 619 nm and favorable Commission Internationale de l'Eclairage coordinates of (0.62, 0.38).

Phenoxazine-Dibenzothiophene Sulfoximine Emitters Featuring Both Thermally Activated Delayed Fluorescence and Aggregation Induced Emission.

In this work, we demonstrate dibenzothiophene sulfoximine derivatives as building blocks for constructing emitters featuring both thermally activated delayed fluorescent (TADF) and aggregation-induced emission (AIE) properties, with multiple advantages including high chemical and thermal stability, facile functionalization, as well as tunable electron-accepting ability. A series of phenoxazine-dibenzothiophene sulfoximine structured TADF emitters were successfully synthesized and their photophysical and electroluminescent properties were evaluated. The electroluminescence devices based on these emitters displayed diverse emissions from yellow to orange and reached external quantum efficiencies (EQEs) of 5.8% with 16.7% efficiency roll-off at a high brightness of 1000 cd·m-2.

A Simple Organic Molecule Realizing Simultaneous TADF, RTP, AIE, and Mechanoluminescence: Understanding the Mechanism Behind the Multifunctional Emitter.

Aggregation-induced emission (AIE), thermally activated delayed fluorescence (TADF), room-temperature phosphorescence (RTP), and mechanoluminescence (ML) have attracted widespread interest. However, a multifunctional organic emitter exhibiting simultaneous AIE, TADF, RTP, and ML has not been reported. Now, two multifunctional blue emitters with very simple structures, mono-DMACDPS and Me-DMACDPS, exhibit typical AIE, TADF, and RTP properties but different behavior in mechanoluminescence. Crystal structure analysis reveals that large dipole moment and multiple intermolecular interactions with tight packing mode endow mono-DMACDPS with strong ML. Combined with the data of crystal analysis and theoretical calculation, the separated monomer and dimer in the crystal lead to the typical TADF and RTP properties, respectively. Simple-structure mono-DMACDPS is the first example realizing TADF, RTP, AIE, and ML simultaneously.

De Novo Design of Excited-State Intramolecular Proton Transfer Emitters via a Thermally Activated Delayed Fluorescence Channel.

Developing excited-state intramolecular proton transfer (ESIPT) emitters with high photoluminescence quantum yields (ΦPLs) and long fluorescence lifetimes in solid state remains a formidable challenge. In this study, we integrated the molecular design tactics of thermally activated delayed fluorescence (TADF) into ESIPT molecules with the goals of improving their ΦPLs and increasing their fluorescence lifetimes. Two proof-of-concept molecules, PXZPDO and DMACPDO, were developed by adopting symmetric D-π-A-π-D molecular architectures (where D and A represent donors and acceptors, respectively) featuring electron-donating phenoxazine or a 9,9-dimethyl-9,10-dihydroacridine moiety, an ESIPT core ß-diketone, and phenylene π-bridges. Both molecules exhibited sole enol-type forms stabilized by intramolecular hydrogen bonds and exhibited a unique and dynamic ESIPT character that was verified by transient absorption analyses. Endowed with distinct TADF features, PXZPDO and DMACPDO showed high ΦPLs of 68% and 86% in the film state, coupled with notable delayed fluorescence lifetimes of 1.33 and 1.94 µs, respectively. Employing these ESIPT emitters successfully achieved maximum external quantum efficiencies (ηexts) of 18.8% and 23.9% for yellow and green organic light-emitting diodes (OLEDs), respectively, which represent the state-of-the-art device performances for ESIPT emitters. This study not only opens a new avenue for designing efficient ESIPT emitters with high ΦPLs and long fluorescence lifetimes in solid state but also unlocks the huge potential of ESIPT emitters in realizing high-efficiency OLEDs.

Optimizing Optoelectronic Properties of Pyrimidine-Based TADF Emitters by Changing the Substituent for Organic Light-Emitting Diodes with External Quantum Efficiency Close to 25 % and Slow Efficiency Roll-Off.

A series of green butterfly-shaped thermally activated delayed fluorescence (TADF) emitters, namely PXZPM, PXZMePM, and PXZPhPM, are developed by integrating an electron-donor (D) phenoxazine unit and electron-acceptor (A) 2-substituted pyrimidine moiety into one molecule via a phenyl-bridge π linkage to form a D-π-A-π-D configuration. Changing the substituent at pyrimidine unit in these emitters can finely tune their emissive characteristics, thermal properties, and energy gaps between the singlet and triplet states while maintaining frontier molecular orbital levels, and thereby optimizing their optoelectronic properties. Employing these TADF emitters results in a green fluorescent organic light-emitting diode (OLED) that exhibits a peak forward-viewing external quantum efficiency (EQE) close to 25 % and a slow efficiency roll-off characteristic at high luminance.

Adamantane-based wide-bandgap host material: blue electrophosphorescence with high efficiency and very high brightness.

An adamantane-based host material, namely, 4-{3-[4-(9H-carbazol-9-yl)phenyl]adamantan-1-yl}benzonitrile (CzCN-Ad), was prepared by linking an electron-donating carbazole unit and an electron-accepting benzonitrile moiety through an adamantane bridge. In this approach, two functional groups were attached to tetrahedral points of adamantane to construct an "sp(3)" topological configuration. This design strategy endows the host material with a high triplet energy of 3.03 eV due to the disruption of intramolecular charge transfer. Although CzCN-Ad has a low molecular weight, the rigid nonconjugated adamantane bridge results in a glass transition temperature of 89 °C. These features make CzCN-Ad suitable for fabricating blue phosphorescent organic light-emitting diodes (PhOLEDs). The devices based on sky-blue phosphor bis[(4,6-difluorophenyl)pyridinato-N,C(2')](picolinato)iridium(III) (FIrpic) achieved a high maximum external quantum efficiency (EQE) of 24.1%, which is among the best results for blue PhOLEDs ever reported. Furthermore, blue PhOLEDs with bis(2,4-difluorophenylpyridinato)-tetrakis(1-pyrazolyl)borate iridium(III) (FIr6) as dopant exhibited a maximum EQE of 14.2% and a maximum luminance of 34 262 cd m(-2). To the best of our knowledge, this is the highest luminance ever reported for FIr6-based PhOLEDs.

In†Situ Solid-State Generation of (BN)2 -Pyrenes and Electroluminescent Devices.

New BN-heterocyclic compounds have been found to undergo double arene photoelimination, forming rare yellow fluorescent BN-pyrenes that contain two BN units. Most significant is the discovery that the double arene elimination can also be driven by excitons generated electrically within electroluminescent (EL) devices, enabling the in situ solid-state conversion of BN-heterocycles to BN-pyrenes and the use of BN-pyrenes as emitters for EL devices. The in situ exciton-driven elimination (EDE) phenomenon has also been observed for other BN-heterocycles.

Luminescent carbene-copper(i)-amide polymers for efficient host-free solution-processed OLEDs.

Luminescent metallopolymers have attracted broad interest in the fields of healthcare and organic electronics. However, polymeric emitters based on earth-abundant metal complexes are scarce. Here, two series of Cu(i) polymers, PMAC-x and PCAAC-x (x = 1-3) have been developed using two kinds of Cu(i)-based carbene-metal-amide (CMA) complexes as side-chain emitter units to combine with a nonconjugated polystyrene backbone. These Cu(i) polymers emit via distinct thermally activated delayed fluorescence or dominant phosphorescence, inherited from the grafted Cu(i)-based CMA units. Particularly, the PMAC-x polymers exhibit high photoluminescence quantum efficiencies of up to 0.78, short emission lifetimes of down to 0.66 µs, and fast radiative rates of up to 106 s-1 in neat films. Thanks to the good encapsulation effect of the polystyrene backbone, these Cu(i) polymers not only demonstrate favorable moisture stability but also show significant aggregation-induced emission. The resultant host-free solution-processed organic light-emitting diodes (OLEDs) achieve outstanding electroluminescence performance with a record external quantum efficiency of 13.8% at a practical luminance of ∼100 nits, representing state-of-the-art device efficiency for metallopolymer-based OLEDs. This work not only presents the first example of CMA polymers but also provides the future direction of polymeric emitters from earth-abundant metal complexes for the OLED application.

Efficient phosphorescent polymer light-emitting diodes by suppressing triplet energy back transfer.

Phosphorescent polymer light-emitting diodes (PhPLEDs) are promising devices in flat panel displays and solid state lighting sources since they can combine the advantages of the high efficiency of electrophosphorescence and low-cost, large-scale manufacture by using a solution process. However, their efficiencies are generally much lower than those of small-molecule-based devices fabricated by using a thermal deposition approach. One of the major reasons for their low efficiency is that energy is lost by back transfer to a polymer host. This tutorial review gives a brief introduction to the fundamentals of PhPLEDs, and then highlights recent progress in the main approaches to suppress triplet energy back transfer from the phosphor to the polymer host towards realizing highly efficient PhPLEDs. The suppressing mechanisms are discussed, and the achievement of high device efficiencies are demonstrated. Emphasis is placed on the relationships between molecular structure, the extent of suppressing triplet energy back transfer, and device performance.

Pivotal role of transition density in circularly polarized luminescence.

Realizing high luminescence dissymmetry factor (g) in circularly polarized luminescence (CPL) materials remains a big challenge, which necessitates understanding systematically how their molecular structure controls the CPL. Here we investigate representative organic chiral emitters with different transition density distributions and reveal the pivotal role of transition density in CPL. We rationalize that to obtain large g-factors, two conditions should be simultaneously satisfied: (i) the transition density for the S1 (or T1)-to-S0 emission must be delocalized over the entire chromophore; and (ii) the chromophore inter-segment twisting must be restricted and tuned to an optimal value (∼50°). Our findings offer molecular-level insights into the CPL of organic emitters, with potential applications in the design of chiroptical materials and systems with strong CPL effects.

Thermally activated delayed fluorescence with dual-emission and pressure-induced bidirectional shifting: cooperative effects of intramolecular and intermolecular energy transfer.

Different from the conventional piezochromic materials with a mono-redshift of single emission, our well-designed molecule demonstrates a sensitive turn-on and color-tunable piezochromic luminescence in response to the hydrostatic pressure. The molecule PXZ-W-SOF possesses dual-emission and pressure-induced bidirectional shifting characteristics. On the basis of in-depth experimental studies, on one hand, it is confirmed that the origin of the dual-emission behavior is the intramolecular charge transfer, namely thermally activated delayed fluorescence (TADF), and the intermolecular excimer; on the other hand, the emission of the excimer exhibits three-step variations with increasing pressure, which is mainly attributed to the molecular structure and its crystal packing state. The remarkable color change of PXZ-W-SOF from sky-blue to green to deep-blue during the whole process of boosting and releasing pressure is a result of intramolecular and intermolecular energy-transfer interactions. The PXZ-W-SOF molecular model is an extremely rare example of highly sensitive fluorescence tuning driven by TADF and excimer conversion under mechanical stimulation, thus providing a novel mechanism for the field of piezochromism. The unique molecular design also offers a new idea for rare deep-blue and ultraviolet TADF materials.