Recent Advances in Structural Design of Efficient Near-Infrared Light-Emitting Organic Small Molecules

Organic light-emitting materials in the near-infrared (NIR) region are important to realize next-generation lightweight and wearable applications in bioimaging, photodynamic therapy, and telecommunications. Inorganic and organometallic light-emitting materials are expensive and toxic; thus, the development of purely organic light-emitting materials is essential. However, the development of highly efficient NIR light-emitting materials made of organic materials is still in its infancy. Therefore, this review outlines molecular design strategies for developing organic small-molecule NIR light-emitting materials with high emission efficiency that can overcome the energy-gap law to be applied to next-generation wearable devices. After briefly reviewing the basic knowledge required for the NIR emission of organic molecules, representative high-efficiency molecules reported over the past 5 years are classified according to their core moieties, and their molecular design, physical properties, and luminescence characteristics are analyzed. Further, the perspective and outlook regarding the development of next-generation high-efficiency NIR organic light-emitting materials are provided.     

Enabling Record-high Deep-Red/Near-Infrared Electroluminescence Through Subtly Managing Intermolecular Interactions of a Thermally Activated Delayed Fluorescence Emitter

Deep-red/near-infrared (DR/NIR) organic light-emitting diodes (OLEDs) are promising for applications such as night-vision readable marking, bioimaging, and photodynamic therapy. To tune emission spectra into the DR/NIR region, red emitters generally require assistance from intermolecular interactions. But such interactions generally lead to sharp efficiency declines resulting from unwanted quenching events. To overcome this challenge, herein, an advanced method via strategically managing the intermolecular interactions of thermally activated delayed fluorescence (TADF) emitters is proposed. The proof-of-concept molecule called DCN-SPTPA exhibits impressive resistance to quenching while delivering controllable aggregation behavior for redshifting the emission by installing an end-spiro group. Consequently, two emitters demonstrate similar photophysical properties and device performance at very low doping levels; while DCN-SPTPA -based OLEDs demonstrate a 1.3–1.4-fold enhancement of the external quantum efficiencies (EQEs) with respect to the control molecule at 5–20 wt.% doping ratios, affording DR/NIR emission at 656, 688, 696, and 716 nm with record-breaking EQEs of 36.1%, 29.3%, 28.2%, and 24.0%, respectively. Moreover, DCN-SPTPA -based nondoped NIR device also retains a state-of-the-art EQE of 2.61% peaked at 800 nm. This work first demonstrates instructive guidance for accurately manipulating the intermolecular interactions of red TADF emitters, which will spur future developments in high-performance DR/NIR OLEDs.     

Copper(I) Complex as Sensitizer Enables High-Performance Organic Light-Emitting Diodes with Very Low Efficiency Roll-Off

Organic light-emitting diodes (OLEDs) utilizing purely organic thermally activated delayed fluorescence (TADF) sensitizers have recently achieved high efficiencies and narrow-band emissions. However, these devices still face intractable challenges of severe efficiency roll-off at practical luminance and finite operational lifetime. Herein, a carbene-Cu(I)-amide complex, (MAC*)Cu(Cz), is demonstrated as a TADF sensitizer for both fluorescent and TADF OLEDs. The (MAC*)Cu(Cz)-sensitized fluorescent OLED not only achieves a high external quantum efficiency (EQE) of 14.6% with an extremely low efficiency roll-off of 12% at the high luminance of 10 000 nits, but also delivers a 15 times longer operational lifetime than that of the non-sensitized reference device. More importantly, utilizing the (MAC*)Cu(Cz) sensitizer in the multi-resonance (MR) TADF OLED results in a record-high EQE of 26.5% together with a full-width at half maximum of 46 nm and an emission peak at 566 nm. This value is the state-of-the-art efficiency for yellow-emitting MR-TADF OLEDs. The photophysical analysis proved that the fast reverse intersystem crossing process of (MAC*)Cu(Cz) is the key factor to suppress triplet exciton involved quenching at high luminance. This finding firstly demonstrates the use of Cu(I) complex as an efficient TADF sensitizer and paves the way for practical applications of TADF sensitized OLEDs.     

Introducing MR-TADF Emitters into Light-Emitting Electrochemical Cells for Narrowband and Efficient Emission

Organic semiconductors that emit by the process of multi-resonance thermally activated delayed fluorescence (MR-TADF) can deliver narrowband and efficient electroluminescence while being processable from solvents and metal-free. This renders them attractive for use as the emitter in sustainable light-emitting electrochemical cells (LECs), but so far reports of narrowband and efficient MR-TADF emission from LEC devices are absent. Here, this issue is addressed through careful and systematic material selection and device development. Specifically, the authors show that the detrimental aggregation tendency of an archetypal rigid and planar carbazole-based MR-TADF emitter can be inhibited by its dispersion into a compatible carbazole-based blend host and an ionic-liquid electrolyte, and it is further demonstrated that the tuning of this active material results in a desired balanced p- and n-type electrochemical doping, a high solid-state photoluminescence quantum yield of 91%, and singlet and triplet trapping on the MR-TADF guest emitter. The introduction of this designed metal-free active MR-TADF material into a LEC, employing air-stabile electrodes, results in bright blue electroluminescence of 500 cd m⁻², which is delivered at a high external quantum efficiency of 3.8% and shows a narrow emission profile with a full-width-at-half-maximum of 31 nm.     

Singlet–Triplet Splitting Energy Management via Acceptor Substitution: Complanation Molecular Design for Deep‐Blue Thermally Activated Delayed Fluorescence Emitters and Organic Light‐Emitting Diodes Application

A barely reached balance between weak intramolecular‐charge‐transfer (ICT) and small singlet–triplet splitting energy (ΔE_ST) for reverse intersystem crossing from non‐emissive triplet state to radiative singlet state impedes the realization of deep‐blue thermally activated delayed fluorescence (TADF) materials. By discarding the twisted‐ICT framework for a flattened molecular backbone and introducing a strong acceptor possessing n–π* transition character, hypsochromic color, a large radiative rate (k_F), and small ΔE_ST are achieved simultaneously. Six molecules with a 9,9‐dimethyl‐10‐phenyl‐9,10‐dihydroacridine (i‐DMAc) donor are synthesized and investigated. Coinciding with time‐dependent density functional theory, the reduced dihedral angles between donor (D) and acceptor (A) weaken ICT from dispersed charge density and enable a large k_F from increased frontier molecular orbitals overlap. Despite the separated highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) population, the intercalation of phenyl bridges between D–A increases k_F but significantly lowers the local triplet excited state, indicating small HOMO and LUMO overlap is not a sufficient, but necessary condition for reduced ΔE_ST. Integrating short conjugation length and carbonyl or triazine acceptors into the complanation molecules, deep‐blue TADF organic light‐emitting diodes demonstrate maximum external quantum efficiencies of 11.5% and 10.9% with Commission Internationale de l'Eclairage coordinates of (0.16, 0.09) and (0.15, 0.11), respectively, which is quite close to the stringent National Television System Committee blue standard.     

Multiresonant Thermally Activated Delayed Fluorescence Emitters Based on Heteroatom‐Doped Nanographenes: Recent Advances and Prospects for Organic Light‐Emitting Diodes

Since the first report in 2015, multiresonant thermally activated delayed fluorescent (MR‐TADF) compounds, a subclass of TADF emitters based on a heteroatom‐doped nanographene material, have come to the fore as attractive hosts as well as emitters for organic light‐emitting diodes (OLEDs). MR‐TADF compounds typically show very narrow‐band emission, high photoluminescence quantum yields, and small ΔE_ST values, typically around 200 meV, coupled with high chemical and thermal stabilities. These materials properties have translated into some of the best reported deep‐blue TADF OLEDs. Here, a detailed review of MR‐TADF compounds and their derivatives reported so far is presented. This review comprehensively documents all MR‐TADF compounds, with a focus on the synthesis, optoelectronic behavior, and OLED performance. In addition, computational approaches are surveyed to accurately model the excited state properties of these compounds.     

Efficient Near-Infrared Organic Light-Emitting Diodes with Emission Peak Above 900 nm Enabled by Enhanced Photoluminescence Quantum Yields and Out-Coupling Efficiencies

Near-infrared organic light-emitting diodes (NIR OLEDs) with emission peak above 900 nm are attractive for many emerging applications, spanning from bioimaging to light detection and ranging. However, the device performance of NIR OLEDs is generally limited by the low quantum efficiency of emitters because of the fast nonradiative transition process imposed by energy-gap law and aggregation quenching. So far, only a few Pt(II) complexes delivering external quantum efficiency (EQE) over 1% are reported, while there is no comparable electroluminescence in heavy-metal-free fluorescent organic emitters. Here, NIR OLEDs centered at 934 nm by blending an acceptor–donor–acceptor type molecule Y11 into a polymer host poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(4,4′-(N-(4-sec-butylphenyl)diphenylamine) (TFB) are reported. The OLEDs show a remarkably high EQE of 1.72%. Moreover, owing to a low turn-on voltage (≈0.9 V), the resultant NIR OLEDs have an electricity-to-light power efficiency surpassing 20 mW W⁻¹. The improved device performance can be attributed to enhanced photoluminescence quantum yields (PLQYs) of the blends owing to suppressed aggregation quenching, and favorable light extraction from the emissive layer. Such values are the highest among fluorescent OLEDs with electroluminescence above 900 nm.     

Indirect Control of Donor/Acceptor Interactions for Highly Efficient Space-Confined Thermally Activated Delayed Fluorescence Emitters

Conformational engineering is essential to further reinforce the luminescent properties of thermally activated delayed fluorescence (TADF) materials featuring through-space charge transfer (TSCT) characteristics. Herein, two TSCT-TADF emitters (8MeDM-B and 8FDM-B) with the methyl and fluorine moieties substituted at the C8 site of the rigid spiro-fluorene bridge is reported. Derivation of the C8 site is first proposed to control the molecular configuration with the ability to indirectly tune the intramolecular interaction between donor and acceptor groups. As a result, 8MeDM-B and 8FDM-B both present small singlet-triplet energy gaps, fast reverse intersystem crossing rates, and high photoluminescence quantum yields. Interestingly, the smaller fluorine atom not the bigger methyl group exhibits more evident electrostatic repulsive force onto the central donor and thus rectifies the central spiro structure. Consequently, the high external quantum efficiency values of 28.8% and 31.7% for 8MeDM-B and 8FDM-B-based electroluminescence devices are achieved, respectively. This study offers a measure for enhancing TSCT-TADF emitters without directly modifying the donor or acceptor.     

Peripheral Decoration of Multi-Resonance Molecules as a Versatile Approach for Simultaneous Long-Wavelength and Narrowband Emission

High device efficiency and color-purity are the two essentials for high-quality organic light-emitting diodes (OLEDs). Multi-resonance (MR) molecules show great potentials for high color-purity OLEDs due to their sharp emission bands. However, most MR molecules exhibit emission limited from deep-blue to green spectral region. Herein, through peripherally decorating MR emitter with electron donors, a new approach enabling the emission spectra of MR emitters red-shift while retaining narrowband emission is demonstrated. By manipulating the numbers and electron-donating abilities of the peripheries, the first narrowband yellow emitter with emission maxima of 562 nm and a full-width at half-maximum (FWHM) of 30 nm is realized. Highly efficient OLEDs with an external quantum efficiency of over 24% and excellent color purity are fabricated by employing these newly developed MR molecules as emitters.     

Efficiency Enhancement of Organic Light‐Emitting Diodes Incorporating a Highly Oriented Thermally Activated Delayed Fluorescence Emitter

An organic light‐emitting diode (OLED) with the blue emitter CC2TA showing thermally activated delayed fluorescence (TADF) is presented exhibiting an external quantum efficiency () of 11% ± 1%, which clearly exceeds the classical limit for fluorescent OLEDs. The analysis of the emission layer by angular dependent photoluminescence (PL) measurements shows a very high degree of 92% horizontally oriented transition dipole moments. Excited states lifetime measurements of the prompt fluorescent component under PL excitation yield a radiative quantum efficiency of 55% of the emitting species. Thus, the radiative exciton fraction has to be significantly higher than 25% due to TADF. Performing a simulation based efficiency analysis for the OLED under investigation allows for a quantification of individual contributions to the efficiency increase originating from horizontal emitter orientation and TADF. Remarkably, the strong horizontal emitter orientation leads to a light‐outcoupling efficiency of more than 30%.     

Novel Deep-Blue Hybridized Local and Charge-Transfer Host Emitter for High-Quality Fluorescence/Phosphor Hybrid Quasi-White Organic Light-Emitting Diode

A new hybrid local and charge transfer (HLCT) molecule 2TPA-PPI is obtained for constructing the high-performance organic light-emitting diodes (OLEDs) in this work. 2TPA-PPI possesses the sufficient emission/charge-transporting properties, thus it is used as a neat emitter achieving an efficient deep-blue OLED with very high external quantum efficiency (EQE) up to 10.7%, as well as a multi-functional emitting host matrix constructing the high-performance phosphorescent OLEDs. More importantly, a high-efficiency candle light-style OLED adopting the HLCT/phosphor hybrid strategy is realized, where 2TPA-PPI acts as not only a blue emitter, but also a universal host sensitizing both yellow and red phosphors. This quasi-white OLED represents almost the highest EQE/PE level of 25.2%/49.7 lm W⁻¹ at the practical luminance level of 1000 cd m⁻² for the white OLEDs with the excellent color rendering index values of more than 80 reported.     

Modulating Backbone Conjugation of Polymeric Thermally Activated Delayed Fluorescence Emitters for High-Efficiency Blue OLEDs

Blue conjugated polymers-based OLEDs with both high efficiency and low efficiency roll-off are under big challenge. Herein, a strategy of local conjugation is proposed to construct high-efficiency blue-emitting conjugated polymers, in which the conjugation degree of polymeric backbones is adjusted by inserting different spacers. In this way, the energy level of triplet state and the energy transfer direction of the polymeric main-chains can be effectively regulated. Benefiting from such fine regulation, the prepared alternative copolymers Alt-PB36 with local conjugated main-chains can better suppress the accumulation of long-lived triplet excitons comparing with the complete conjugated polymers. The higher PLQY of Alt-PB36 also verifies the effective energy transfer from the polymeric main-chains to the TADF units. Accordingly, Alt-PB36 based solution-processed OLEDs achieve an EQE_max of 11.6% and a very low efficiency roll-off of 2.8% at 100 cd m⁻² and 15.2% at 500 cd m⁻². This result represents the best efficiency among blue light-emitting conjugated polymer-based OLEDs so far under high luminance.     

“Trade‐Off” Hidden in Condensed State Solvation: Multiradiative Channels Design for Highly Efficient Solution‐Processed Purely Organic Electroluminescence at High Brightness

Actualizing highly efficient solution‐processed thermally activated delayed fluorescent (TADF) organic light‐emitting diodes (OLEDs) at high brightness becomes significant to the popularization of purely organic electroluminescence. Herein, a highly soluble emitter benzene‐1,3,5‐triyltris((4‐(9,9‐dimethylacridin‐10(9H)‐yl)phenyl)methanone was developed, yielding high delayed fluorescence rate (k_TADF > 10⁵ s^?1) ascribed to the multitransition channels and tiny singlet–triplet splitting energy (ΔE_ST ≈ 32.7 meV). The triplet locally excited state is 0.38 eV above the lowest triplet charge‐transfer state, assuring a solely thermal equilibrium route for reverse intersystem crossing. Condensed state solvation effect unveils a hidden “trade‐off”: the reverse upconversion and triplet concentration quenching processes can be promoted but with a reduced radiative rate from the increased dopant concentration and the more polarized surroundings. Striking a delicate balance, corresponding vacuum‐evaporated and solution‐processed TADF‐OLEDs realized maximum external quantum efficiencies (EQEs) of ≈26% and ≈22% with extremely suppressed efficiency roll‐off. Notably, the wet‐processed one achieves to date the highest EQEs of 20.7%, 18.5%, 17.1%, and 13.6%, among its counterparts at the luminance of 1000, 3000, 5000, and 10 000 cd m^?2, respectively.     

Triphenylamine-Functionalized Multiple-Resonance TADF Emitters with Accelerated Reverse Intersystem Crossing and Aggregation-Induced Emission Enhancement for Narrowband OLEDs

Multiple-resonance (MR) thermal activated delayed fluorescence (TADF) emitters have attracted increasing attention in organic electroluminescence devices, owing to their superior quantum efficiency and narrowband emission for high color purity. However, MR-TADF materials often suffer from severe aggregation-caused quenching (ACQ) and efficiency roll-off problems due to their rigid planar structures and the lack of sufficient charge-transfer (CT) characters with inefficient reverse intersystem crossing (RISC). Herein, by attaching electron-rich triphenylamine (TPA) with twisted spatial conformation to the MR framework, two efficient narrowband MR-TADF emitters, namely BNCz-pTPA and BNCz-mTPA , are developed. The TPA substituent endows the new emitters with aggregation-induced emission enhancement (AIEE) for ACQ suppression. The unprecedented AIEE-MR-TADF emitters exhibit CT character in high-lying triplet excited states for faster RISC, while the locally-excited (LE) character of the first singlet excited state is retained for narrowband emission with high emission efficiency. An organic light-emitting diode (OLED) based on BNCz-pTPA exhibits a maximum external quantum efficiency of 27.3% with slow efficiency roll-off, demonstrating much higher performances than those of the BNCz -based OLED. This study may provide a simple but effective approach to constructing high-performance emitters for wide-color-gamut OLED displays.     

Manipulating Complementarity of Binary White Thermally Activated Delayed Fluorescence Systems for 100% Exciton Harvesting in OLEDs

Different to fluorescent and phosphorescent counterparts, white thermally activated delayed fluorescence (TADF) involves in multiple reverse intersystem crossing (RISC), leading to the correlation but competition between blue and other color components in both singlet and triplet allocations. Herein, three blue TADF emitters SSFAPO, DSFAPO, and TSFAPO, collectively named xSFAPO are developed, featuring a moderately electron-withdrawing phosphine oxide (PO) acceptor respectively linked 1-3 donors. Despite nearly identical blue emissions, photoluminescence quantum yields of xSFAPO are proportional to donor number. But, their RISC efficiencies are below 70%, markedly less than 85% of a conventional yellow TADF emitter 2,3,5,6-tetrakis(3,6-di-(tert-butyl)carbazol-9-yl)-1,4-dicyanobenzene (4CzTPNBu). Furthermore, sp³ hybrid configuration of PO enlarges steric hindrance of peripheral donor groups. So, Dexter energy transfer is impeded by increasing donor numbers. Among xSFAPO and 4CzTPNBu dually doped white-emitting films, yellow emission from SSFAPO-based film is the strongest, reflecting the predominance of fast Dexter energy transfer in triplet allocation. Therefore, SSFAPO endowed its warm-white organic light-emitting diodes (WOLEDs) with an external quantum efficiency of 25.1%, corresponding to 100% internal quantum efficiency, which are 1.25 and 1.60 folds of those of DSFAPO and TSFAPO-based WOLEDs. These results suggest advantage complementarity of different components is crucial for developing white-emitting systems with 100% exciton utilization.     

High‐Performance Hybrid White Organic Light‐Emitting Diodes with Superior Efficiency/Color Rendering Index/Color Stability and Low Efficiency Roll‐Off Based on a Blue Thermally Activated Delayed Fluorescent Emitter

Thermally activated delayed fluorescence (TADF)‐based white organic light‐emitting diodes (WOLEDs) are highly attractive because the TADF emitters provide a promising alternative route to harvest triplet excitons. One of the major challenges is to achieve superior efficiency/color rendering index/color stability and low efficiency roll‐off simultaneously. In this paper, high‐performance hybrid WOLEDs are demonstrated by employing an efficient blue TADF emitter combined with red and green phosphorescent emitters. The resulting WOLED shows the maximum external quantum efficiency, current efficiency, and power efficiency of 23.0%, 51.0 cd A^?1, and 51.7 lm W^?1, respectively. Moreover, the device exhibits extremely stable electroluminescence spectra with a high color rendering index of 89 and Commission Internationale de L'Eclairage coordinates of (0.438, 0.438) at the practical brightness of 1000 cd m^?2. The achievement of these excellent performances is systematically investigated by versatile experimental and theoretical evidences, from which it is concluded that the utilization of a blue‐green‐red cascade energy transfer structure and the precise manipulation of charges and excitons are the key points. It can be anticipated that this work might be a starting point for further research towards high‐performance hybrid WOLEDs.     

High‐Efficiency Near‐Infrared Fluorescent Organic Light‐Emitting Diodes with Small Efficiency Roll‐Off: A Combined Design from Emitters to Devices

The simultaneous realization of high quantum yield and exciton utilizing efficiency (η_r) is still a formidable challenge in near‐infrared (NIR) fluorescent organic light‐emitting diodes (FOLEDs). Here, to achieve a high quantum yield, a novel NIR dye, 4,9‐bis(4‐(diphenylamino)phenyl)‐naphtho[2,3‐c ][1,2,5]selenadiazole, is designed and synthesized with a large highest occupied molecular orbital/lowest unoccupied molecular orbital overlap and an aggregation‐induced emission property, which demonstrates a high photoluminescence quantum yield of 27% at 743 nm in toluene and 29% at 723 nm in a blend film. For a high η_r, an orange‐emitting thermally activated delayed fluorescent material, 1,2‐bis(9,9‐dimethyl‐9,10‐dihydroacridine)‐4,5‐dicyanobenzene, is chosen as the sensitizing host to harvest triplet excitons in devices. The optimized devices achieve a good η_r of 45.7% and a high external quantum efficiency up to 2.65% at 730 nm, with a very small efficiency roll‐off of 2.41% at 200 mA cm^?2, which are among the most efficient values for NIR‐FOLEDs over 700 nm. The effective utilization of triplet excitons via the thermally activated delayed fluorescence‐sensitizing host will pave a way to realize high‐efficiency NIR‐FOLEDs with small efficiency roll‐off.     

Exciton‐Adjustable Interlayers for High Efficiency,Low Efficiency Roll‐Off,and Lifetime Improved Warm White Organic Light‐Emitting Diodes (WOLEDs) Based on a Delayed Fluorescence Assistant Host

Recently, a new route to achieve 100% internal quantum efficiency white organic light‐emitting diodes (WOLEDs) is proposed by utilizing noble‐metal‐free thermally activated delayed fluorescence (TADF) emitters due to the radiative contributions of triplet excitons by effective reverse intersystem crossing. However, a systematic understanding of their reliability and internal degradation mechanisms is still deficient. Here, it demonstrates high performance and operational stable purely organic fluorescent WOLEDs consisting of a TADF assistant host via a strategic exciton management by multi‐interlayers. By introducing such interlayers, carrier recombination zone could be controlled to suppress the generally unavoidable quenching of long‐range triplet excitons, successfully achieving remarkable external quantum efficiency of 15.1%, maximum power efficiency of 48.9 lm W⁻¹, and extended LT50 lifetime (time to 50% of initial luminance of 1000 cd m⁻²) exceeding 2000 h. To this knowledge, this is the first pioneering work for realizing high efficiency, low efficiency roll‐off, and operational stable WOLEDs based on a TADF assistant host. The current findings also indicate that broadening the carrier recombination region in both interlayers and yellow emitting layer as well as restraining exciplex quenching at carrier blocking interface make significant roles on reduced efficiency roll‐off and enhanced operational lifetime.     

High‐Performance Dibenzoheteraborin‐Based Thermally Activated Delayed Fluorescence Emitters: Molecular Architectonics for Concurrently Achieving Narrowband Emission and Efficient Triplet–Singlet Spin Conversion

Thermally activated delayed fluorescence (TADF) materials, which enable the full harvesting of singlet and triplet excited states for light emission, are expected as the third‐generation emitters for organic light‐emitting diodes (OLEDs), superseding the conventional fluorescence and phosphorescence materials. High photoluminescence quantum yield (Φ_PL), narrow‐band emission (or high color purity), and short delayed fluorescence lifetime are all strongly desired for practical applications. However, to date, no rational design strategy of TADF emitters is established to fulfill these requirements. Here, an epoch‐making design strategy is proposed for producing high‐performance TADF emitters that concurrently exhibiting high Φ_PL values close to 100%, narrow emission bandwidths, and short emission lifetimes of ≈1 µs, with a fast reverse intersystem crossing rate of over 10⁶ s^?1. A new family of TADF emitters based on dibenzoheteraborins is introduced, which enable both doped and non‐doped TADF‐OLEDs to achieve markedly high external electroluminescence quantum efficiencies, exceeding 20%, and negligible efficiency roll‐offs at a practical high luminance. Systematic photophysical and theoretical investigations and device evaluations for these dibenzoheteraborin‐based TADF emitters are reported here.     

Improving the Efficiency of Red Thermally Activated Delayed Fluorescence Organic Light‐Emitting Diode by Rational Isomer Engineering

The development of efficient red thermally activated delayed fluorescence (TADF) emitters with an emission wavelength beyond 600 nm remains a great challenge for organic light‐emitting diodes (OLEDs). Herein, two pairs of isomers are designed and synthesized by attaching electron‐donor 9,9‐diphenyl‐9,10‐dihydroacridine (DPAC) moiety to the different positions of two kinds of highly rigid planar acceptor cores (PDCN and PPDCN). Their TADF efficiencies and emission maxima (599–726 nm) are regulated by molecular isomer manipulation. Interestingly, the photoluminescence quantum yields (Φ_PLs) of trans‐isomers T‐DA‐1 and T‐DA‐2 (78% and 89%) are remarkably higher than those of their corresponding cis‐isomers C‐DA‐1 and C‐DA‐2 (12% and 14%). Significantly increased Φ_PL values can be explained by single crystal structures and theoretical simulation. As a result, a deep red TADF‐OLED based on T‐DA‐2 displays a maximum external quantum efficiency (EQE) of 26.26% at 640 nm. Notably, at a brightness of 100 cd m^?2, the EQE value of T‐DA‐2‐based device still remains at an extremely high level of 23.95%, representing the highest value for reported red TADF‐OLEDs at the same brightness. These results provide a reasonable pathway to optimize optoelectronic properties and thereby construct efficient red TADF emitters through rational isomer engineering.