Synthesis of Linear and V-Shaped Carbazolyl-Substituted Pyridine-3,5-dicarbonitriles Exhibiting Efficient Bipolar Charge Transport and E-Type Fluorescence

With the aim of developing all-organic bipolar semiconductors with high charge mobility and efficient E-type fluorescence (so-called TADF) as environmentally friendly light-emitting materials for optoelectronic applications, four noble metals-free dyes with linear and V-shapes were designed using accepting pyridine-3,5-dicarbonitrile and donating carbazole units. By exploiting a donor-acceptor design strategy and using moieties with different donating and accepting abilities, TADF emitters with a wide variety of molecular weights were synthesized to achieve the optimum combination of charge-transporting and fluorescent properties in one TADF molecule. Depending on molecule structures, different TADF emitters capable of emitting in the range from 453 to 550 nm with photoluminescence quantum yields up to 98 % for the solutions in oxygen-free toluene were obtained. All compounds showed bipolar charge-transport. Hole mobility of 2.8×10⁻³ cm²/Vs at 7×10⁵ V cm⁻¹ was observed for the compound containing two di-tert-butyl-substituted carbazole moieties. The compounds were tested in both non-doped and doped organic light-emitting diodes using different hosts. It was shown that the developed TADF emitters are suitable for different color devices with electroluminescence ranging from blue to yellow and with brightness, maximum current and external quantum efficiencies exceeding 10 000 cd m⁻², 15 cd/A, and 7 %, respectively.     

Strongly Luminescent Tungsten Emitters with Emission Quantum Yields of up to 84 %: TADF and High‐Efficiency Molecular Tungsten OLEDs

Metal‐TADF (thermally activated delayed fluorescence) emitters hold promise in the development of next generation light‐emitting materials for display and lighting applications, examples of which are, however, largely confined to Cu^I and recently Au^I, Ag^I, and Au^III emitters. Herein is described the design strategy for an unprecedented type of metal‐TADF emitter based on inexpensive tungsten metal chelated with Schiff base ligand that exhibit high emission quantum yields of up to 56 % in solutions and 84 % in thin‐film (5 wt % in 1,3‐bis(N‐carbazolyl)benzene, mCP) at room temperature. Femtosecond time‐resolved emission (fs‐TRE) spectroscopy and DFT calculations were undertaken to decipher the TADF properties. Solution‐processed OLEDs fabricated with the W‐TADF emitter demonstrated external quantum efficiency (EQE) and luminance of up to 15.6 % and 16890 cd m^?2, respectively.     

Donor–σ–Acceptor Motifs: Thermally Activated Delayed Fluorescence Emitters with Dual Upconversion

A family of organic emitters with a donor–σ–acceptor (D‐σ‐A) motif is presented. Owing to the weakly coupled D‐σ‐A intramolecular charge‐transfer state, a transition from the localized excited triplet state (³LE) and charge‐transfer triplet state (³CT) to the charge‐transfer singlet state (¹CT) occurred with a small activation energy and high photoluminescence quantum efficiency. Two thermally activated delayed fluorescence (TADF) components were identified, one of which has a very short lifetime of 200–400 ns and the other a longer TADF lifetime of the order of microseconds. In particular, the two D‐σ‐A materials presented strong blue emission with TADF properties in toluene. These results will shed light on the molecular design of new TADF emitters with short delayed lifetimes.     

Controlling Singlet–Triplet Energy Splitting for Deep‐Blue Thermally Activated Delayed Fluorescence Emitters

The development of efficient metal‐free organic emitters with thermally activated delayed fluorescence (TADF) properties for deep‐blue emission is still challenging. A new family of deep‐blue TADF emitters based on a donor–acceptor architecture has been developed. The electronic interaction between donor and acceptor plays a key role in the TADF mechanism. Deep‐blue OLEDs fabricated with these TADF emitters achieved high external quantum efficiencies over 19.2 % with CIE coordinates of (0.148, 0.098).     

Tetradentate Gold(III) Complexes as Thermally Activated Delayed Fluorescence (TADF) Emitters: Microwave‐Assisted Synthesis and High‐Performance OLEDs with Long Operational Lifetime

Structurally robust tetradentate gold(III)‐emitters have potent material applications but are rare and unprecedented for those displaying thermally activated delayed fluorescence (TADF). Herein, a novel synthetic route leading to the preparation of highly emissive, charge‐neutral tetradentate [C^C^N^C] gold(III) complexes with 5‐5‐6‐membered chelate rings has been developed through microwave‐assisted C?H bond activation. These complexes show high thermal stability and with emission origin (³IL, ³ILCT, and TADF) tuned by varying the substituents of the C^C^N^C ligand. With phenoxazine/diphenylamine substituent, we prepared the first tetradentate gold(III) complexes that are TADF emitters with emission quantum yields of up to 94 % and emission lifetimes of down to 0.62 μs in deoxygenated toluene. These tetradentate Au^III TADF emitters showed good performance in vacuum‐deposited OLEDs with maximum EQEs of up to 25 % and LT₉₅ of up to 5280 h at 100 cd m^?2.     

Rational Molecular Design Overcoming the Long Delayed Fluorescence Lifetime and Serious Efficiency Roll-Off in Blue Thermally Activated Delayed Fluorescent Devices

Blue thermally activated delayed fluorescent (TADF) devices with short excited-state lifetime, high reverse intersystem crossing rate, and low-efficiency roll-off were developed by managing the molecular structure of donor–acceptor-type blue emitters. Three isomers of blue TADF emitters with a diphenyltriazine acceptor and three carbazole donors were synthesized. The position of the donor moieties in the phenyl linker connecting the donor and acceptor moieties was controlled to devise compounds with a short delayed fluorescence lifetime. A blue TADF emitter with three carbazole donors at 2-, 3-, and 4- positions of a phenyl linker shortened the excited state lifetime to 4.1 μs, showed a high external quantum efficiency of 20.4 %, and low efficiency roll-off of less than 10 % at 1000 cd m⁻². Therefore, a molecular design distorting the donors by aligning them in a consecutive way is useful to resolve the issues of long delayed fluorescence lifetime and efficiency roll-off of blue TADF devices.     

Tetradentate Gold(III) Complexes as Thermally Activated Delayed Fluorescence (TADF) Emitters: Microwave-Assisted Synthesis and High-Performance OLEDs with Long Operational Lifetime

Structurally robust tetradentate gold(III)-emitters have potent material applications but are rare and unprecedented for those displaying thermally activated delayed fluorescence (TADF). Herein, a novel synthetic route leading to the preparation of highly emissive, charge-neutral tetradentate [C^C^N^C] gold(III) complexes with 5-5-6-membered chelate rings has been developed through microwave-assisted C−H bond activation. These complexes show high thermal stability and with emission origin (³IL, ³ILCT, and TADF) tuned by varying the substituents of the C^C^N^C ligand. With phenoxazine/diphenylamine substituent, we prepared the first tetradentate gold(III) complexes that are TADF emitters with emission quantum yields of up to 94 % and emission lifetimes of down to 0.62 μs in deoxygenated toluene. These tetradentate Au^III TADF emitters showed good performance in vacuum-deposited OLEDs with maximum EQEs of up to 25 % and LT₉₅ of up to 5280 h at 100 cd m⁻².     

Acceptor modulation for improving thermally activated delayed fluorescence emitter in through-space charge transfer on spiroskeletons

Through-space charge transfer (TSCT) is regarded as an effective way to develop thermally activated delayed fluorescence (TADF) emitters. Based on this strategy, many molecular frameworks have been proposed, among which spirobased scaffolds have been extensively studied due to their unique advantages. In this work, we developed three emitters SPS, SPO, and SPON, which were constructed with the same donor and various acceptors to explore the influence of acceptor modulation at the C9 position of fluorene for spirostructure TSCT emitters. The results show that the acceptor with too weak electron-withdrawing ability will cause the emitter to not have TADF properties, while the acceptor with too much steric hindrance will weaken the face-to-face π-π stacking interaction between donor/acceptor (D/A). Since SPO balances the electron-withdrawing strength and steric hindrance of the acceptor, it achieves the highest external quantum efficiency (EQE) of 17.75%. This work shows that appropriate acceptor selection is essential for the TADF properties and high efficiency of the spirobased scaffold TSCT emitter     

Combining Carbazole Building Blocks and ν-DABNA Heteroatom Alignment for a Double Boron-Embedded MR-TADF Emitter with Improved Performance

Building blocks and heteroatom alignments are two determining factors in designing multiple resonance (MR)-type thermally activated delayed fluorescence (TADF) emitters. Carbazole-fused MR emitters, represented by CzBN derivatives, and the heteroatom alignments of ν-DABNA are two star series of MR-TADF emitters that show impressive performances from the aspects of building blocks and heteroatom alignments, respectively. Herein, a novel CzBN analog, Π-CzBN, featuring ν-DABNA heteroatom alignment is developed via facile one-shot lithium-free borylation. Π-CzBN exhibits superior photophysical properties with a photoluminescence quantum yield close to 100 % and narrowband sky blue emission with a full width at half maximum (FWHM) of 16 nm/85 meV. It also gives efficient TADF properties with a small singlet-triplet energy offset of 40 meV and a fast reverse intersystem crossing rate of 2.9×10⁵ s⁻¹. The optimized OLED using Π-CzBN as the emitter achieves an exceptional external quantum efficiency of 39.3 % with a low efficiency roll-off of 20 % at 1000 cd m⁻² and a narrowband emission at 495 nm with FWHM of 21 nm/106 meV, making it one of the best reported devices based on MR emitters with comprehensive performance.     

Narrowband blue emission with insensitivity to the doping concentration from an oxygen-bridged triarylboron-based TADF emitter: nondoped OLEDs with a high external quantum efficiency up to 21.4%

Blue thermally activated delayed fluorescence (TADF) emitters that can simultaneously achieve narrowband emission and high efficiency in nondoped organic light-emitting diodes (OLEDs) remain a big challenge. Herein, we successfully design and synthesize two blue TADF emitters by directly incorporating carbazole fragments into an oxygen-bridged triarylboron acceptor. Depending on the linking mode, the two emitters show significantly different photophysical properties. Benefitting from the bulky steric hindrance between the acceptor and terminal pendants, the blue emitter TDBA-Cz exhibited a high photoluminescence quantum yield (PLQY) of 88% in neat films and narrowband emission. The corresponding non-doped blue device exhibited a maximum external quantum efficiency (EQE) of 21.4%, with a full width at half maximum (FWHM) of only 45 nm. This compound is the first blue TADF emitter that can concurrently achieve narrow bandwidth and high electroluminescence (EL) efficiency in nondoped blue TADF-OLEDs.

A donor–acceptor TADF emitter showed narrowband high-efficiency blue emission by fine molecular modulation. The corresponding OLEDs exhibited a maximum EQE of 21.4% and a small FWHM of 45 nm, representing the most efficient nondoped blue TADF-OLEDs.     

A Methodological Study on Tuning the Thermally Activated Delayed Fluorescent Performance by Molecular Constitution in Acridine–Benzophenone Derivatives

Thermally activated delayed fluorescent (TADF) emitters are usually designed as donor–acceptor structures with large dihedral angles, which tend to incur low fluorescent efficiency, and therefore, through molecular design various strategies have been proposed to increase the efficiency of emitters; however, few studies have compared these strategies in one TADF system. In this study, a novel TADF molecule, [4‐(9,9‐diphenylacridin‐10‐yl)phenyl](phenyl)methanone ( BP‐DPAC ), was designed as a prototype, and two derivatives, BP‐Ph‐DPAC and DPAC‐BP‐DPAC , were also prepared to represent two common approaches to enhance TADF performance. Compared with the maximum external quantum efficiency (EQE) of 6.82 % for BP‐DPAC , organic light‐emitting diodes (OLED) devices based on DPAC‐BP‐DPAC exhibited enhanced TADF properties with the highest maximum EQE of 18.67 %, owing to an additional diphenylacridine donor, whereas BP‐Ph‐DPAC showed non‐TADF properties and exhibited the lowest EQE of 4.25 %, owing to the insertion of a phenyl ring between donor and acceptor.     

TADF-Sensitized Fluorescent Enantiomers: A New Strategy for High-Efficiency Circularly Polarized Electroluminescence**

A promising strategy of thermally activated delayed fluorescence (TADF) sensitized circularly polarized luminescence (CPL) has been proposed for improving the electroluminescence efficiencies of circularly polarized fluorescent emitters. Compared with chiral TADF emitters which suffer from the dilemma of small ΔE_ST accompanied by small k_r, the TADF-sensitized CPL (TSCP) strategy using TADF molecules as sensitizers and CP-FL molecules as emitters might be the most promising method to construct high-performance circularly polarized organic light-emitting diodes (CP-OLEDs). Consequently, by taking advantage of the theoretically 100 % exciton utilization of TADF sensitizers, especially, by designing CP-FL emitters with high PLQY, narrow FWHM and large g_lum values, TSCP-type CP-OLEDs with excellent overall performances can be realized.     

Asymmetric Spirobiacridine-based Delayed Fluorescence Emitters for High-performance Organic Light-Emitting Devices

Recently, researchers have focused on thermally activated delayed fluorescence (TADF) for efficient future lighting and displays. Among TADF emitters, a combination of triazine and acridine is a promising candidate for realizing high-efficiency organic light-emitting devices (OLEDs). However, simultaneous development of perfect horizontal orientation (Θ=100 %) and an external quantum efficiency (EQE) of over 40 % is still challenging. Here, to obtain insights for further improvements of a triazine/acridine combination, various asymmetric spirobiacridine (SBA)-based TADF emitters with a unity photoluminescence quantum yield and high Θ ratio of over 80 % were developed. Furthermore, the substitution effects of the triazine acceptor unit on the photophysical properties were studied, including molecular orientations and OLED performance. The corresponding OLED exhibited sky-blue emission with a high EQE of over 30 %.     

Using fluorene to lock electronically active moieties in thermally activated delayed fluorescence emitters for high-performance non-doped organic light-emitting diodes with suppressed roll-off

Thermally activated delayed fluorescence (TADF) emitters with aggregation-induced emission (AIE) features are hot candidates for non-doped organic light-emitting diodes (OLEDs), as they are highly emissive in solid states upon photoexcitation. Nevertheless, not every AIE-TADF emitter in the past had guaranteed decent efficiencies in non-doped devices, indicating that the AIE character alone does not necessarily afford ideal non-doped TADF emitters. As intermolecular electron-exchange interaction that involves long-lived triplet excitons plays a dominant role in the whole quenching process of TADF, we anticipate that it is the main reason for the different electroluminescence performances of AIE-TADF emitters. Therefore, in this work, we designed two TADF emitters SPBP-DPAC and SPBP-SPAC by modifying a reported less successful emitter BP-DPAC with extra fluorenes to increase intermolecular distances and attenuate this electron-exchange interaction. With the fluorene lock as steric hindrance, SPBP-DPAC and SPBP-SPAC exhibit significantly higher exciton utilization in non-doped films due to the suppressed concentration quenching. The non-doped OLEDs based on SPBP-DPAC and SPBP-SPAC show an excellent maximum external quantum efficiency (EQE) of 22.8% and 21.3% respectively, and what''s even more promising is that ignorable roll-offs at practical brightness (e.g., 1000 and 5000 cd m⁻²) were realized. These results reveal that locking the phenyl rings as steric hindrance can not only enhance the molecular rigidity, but also cause immediate relief of concentration quenching, and result in significant performance improvement under non-doped conditions. Our approach proposes a feasible molecular modification strategy for AIE-TADF emitters, potentially increasing their applicability in OLEDs.

Two TADF emitters were developed by modifying a reported less successful emitter BP-DPAC with fluorene to suppress concentration quenching. Their non-doped OLEDs displayed excellent EQEs of 22.8% and 21.3% with well-suppressed roll-off.     

Dibenzo[a,j]phenazine‐Cored Donor–Acceptor–Donor Compounds as Green‐to‐Red/NIR Thermally Activated Delayed Fluorescence Organic Light Emitters

A new family of thermally activated delayed fluorescence (TADF) emitters based on U‐shaped D‐A‐D architecture with a novel accepting unit has been developed. All investigated compounds have small singlet‐triplet energy splitting (ΔE_ST) ranging from 0.02 to 0.20 eV and showed efficient TADF properties. The lowest triplet state of the acceptor unit plays the key role in the TADF mechanism. OLEDs fabricated with these TADF emitters achieved excellent efficiencies up to 16 % external quantum efficiency (EQE).     

Highly Efficient Au(I) Alkynyl Emitters: Thermally Activated Delayed Fluorescence and Solution-Processed OLEDs

Two-coordinate donor-metal-acceptor type coinage metal complexes displaying efficient thermally activated delayed fluorescence (TADF) have been unveiled to be highly appealing candidates as emitters for organic light-emitting diodes (OLEDs). Herein a series of green to yellow TADF gold(I) complexes with alkynyl ligands has been developed for the first time. The complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 0.76 in doped films (5 wt % in PMMA) at room temperature. The modifications of alkynyl ligands with electron-donating amino groups together with the use of electron-deficient carbene ligands induce ligand-to-ligand charge transfer excited states that give rise to TADF emission. Spectroscopic and density functional theory (DFT) calculations reveal the roles of electron-donating capability of the alkynyl ligand in tuning the excited-state properties. Solution-processed organic light-emitting diodes (OLEDs) using the present complexes as emitters achieve maximum external quantum efficiency (EQE) of up to 20 %.     

CN-Modified Imidazopyridine as a New Electron Accepting Unit of Thermally Activated Delayed Fluorescent Emitters

Two efficient thermally activated delayed fluorescent (TADF) emitters were developed by utilizing CN-modified imidazopyridine as an acceptor unit. The CN-modified imidazopyridine acceptor was combined with either an acridine donor or a phenoxazine donor through a phenyl linker to produce two TADF emitters, Ac-CNImPy and PXZ-CNImPy. The acridine-based Ac-CNImPy emitter exhibited sky-blue emission with a CIE coordinate of (0.18, 0.38), whereas the phenoxazine-donor-based PXZ-CNImPy showed greenish-yellow emission with a CIE coordinate of (0.32, 0.58). A high photoluminescence quantum yield of 80 % was observed for the PXZ-CNImPy emitter compared with 40 % for the Ac-CNImPy emitter. Organic light-emitting diodes based on the PXZ-CNImPy emitter demonstrated high external quantum efficiency of 17.0 %. Hence, the CN-modified imidazopyridine unit can be considered as a useful electron acceptor for the future design of highly efficient TADF emitters.     

Constructing a Novel Dendron for a Self‐Host Blue Emitter with Thermally Activated Delayed Fluorescence: Solution‐Processed Nondoped Organic Light‐Emitting Diodes with Bipolar Charge Transfer and Stable Color Purity

Self‐host thermally activated delayed fluorescence (TADF) materials have recently been identified as effective emitters for solution‐processed nondoped organic light‐emitting diodes (OLEDs). However, except for the carbazole unit, few novel dendrons have been developed to build self‐host TADF emitters. This study reports two self‐host blue materials, tbCz‐SO and poCz‐SO, with the same TADF emissive core and different dendrons. The influence of the peripheral dendrons on the photophysical properties and electroluminescent performances of the self‐host materials were systematically investigated. The transient fluorescence and electroluminescence spectra indicated that the diphenylphosphoryl carbazole units could effectively encapsulate the emissive core to reduce the concentration quenching effect and to enhance reverse intersystem crossing. By using tbCz‐SO and poCz‐SO as host‐free blue emitters, the performance of the solution‐processed nondoped OLED device demonstrated that a more balanced charge transfer from the bipolar dendrons would offer a better current efficiency of 10.5 cd A⁻¹ and stable color purity with Commission Internationale de L'Eclairage units of (0.18, 0.27).     

Multi‐Resonance Induced Thermally Activated Delayed Fluorophores for Narrowband Green OLEDs

High‐color‐purity emissions with small a full‐width at half‐maximum (FWHM) are an ongoing pursuit for high‐resolution displays. Though the flourishment of narrow‐band emissive materials with multi‐resonance induced thermally activated delayed fluorescence (MR‐TADF) in the blue region, such materials have not validated their potential in other color regions. By amplifying the influence of skeleton and peripheral units, a series of highly efficient green‐emitting MR‐TADF materials are firstly reported. Peripheral units with electron‐deficit properties can significantly narrow the energy gap for bathochromic emission without compromising the color fidelity. MR‐TADF emitters with photo‐luminance quantum yields of above 90 % with FWHMs of ≤25 nm are developed. The corresponding organic light‐emitting diodes show maximum external quantum efficiency/ power efficiency of 22.02 %/ 69.82 lm W^?1 with excellent long‐term stability.     

Tri‐Spiral Donor for High Efficiency and Versatile Blue Thermally Activated Delayed Fluorescence Materials

Blue thermally activated delayed fluorescence (TADF) emitters that can simultaneously achieve high efficiency in doped and nondoped organic light‐emitting diodes (OLEDs) are rarely reported. Reported here is a strategy using a tri‐spiral donor for such versatile blue TADF emitters. Impressively, by simply extending the nonconjugated fragment and molecular length, aggregation‐caused emission quenching (ACQ) can be greatly alleviated to achieve as high as a 90 % horizontal orientation dipole ratio and external quantum efficiencies (EQEs) of up to 33.3 % in doped and 20.0 % in nondoped sky‐blue TADF‐OLEDs. More fascinatingly, a high‐efficiency purely organic white OLED with an outstanding EQE of up to 22.8 % was also achieved by employing TspiroS‐TRZ as a blue emitter and an assistant host. This compound is the first blue TADF emitter that can simultaneously achieve high electroluminescence (EL) efficiency in doped, nondoped sky‐blue, and white TADF‐OLEDs.