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Since the seminal report by Adachi and co-workers in 2012, there has been a veritable explosion of interest in the design of thermally activated delayed fluorescence (TADF) compounds, particularly as emitters for organic light-emitting diodes (OLEDs). With rapid advancements and innovation in materials design, the efficiencies of TADF OLEDs for each of the primary color points as well as for white devices now rival those of state-of-the-art phosphorescent emitters. Beyond electroluminescent devices, TADF compounds have also found increasing utility and applications in numerous related fields, from photocatalysis, to sensing, to imaging and beyond. Following from our previous review in 2017 ( Adv. Mater. 2017, 1605444), we here comprehensively document subsequent advances made in TADF materials design and their uses from 2017-2022. Correlations highlighted between structure and properties as well as detailed comparisons and analyses should assist future TADF materials development. The necessarily broadened breadth and scope of this review attests to the bustling activity in this field. We note that the rapidly expanding and accelerating research activity in TADF material development is indicative of a field that has reached adolescence, with an exciting maturity still yet to come.

Here the utility and potential of an emitter design are demonstrated, consisting of a narrowband-emitting multiresonant thermally activated delayed fluorescent (MR-TADF) core that is decorated with a suitably higher energy donor-acceptor TADF moiety. Not only does this D-A TADF group offer additional channels for triplet exciton harvesting and confers faster reverse intersystem crossing (RISC) kinetics but it also acts as a steric shield, insulating the emissive MR-TADF core from aggregation-caused quenching. Two emitters, DtCzBN-CNBT1 and DtCzBN-CNBT2, demonstrate enhanced photophysical properties leading to outstanding performance of the organic light-emitting diodes (OLEDs). DtCzBN-CNBT2, containing a D-A TADF moiety, has a faster k RISC (1.1 × 10 5 s -1 ) and higher photoluminescence quantum yield (Φ PL : 97%) compared to DtCzBN-CNBT1 (0.2 × 10 5 s -1 , Φ PL : 90%), which contains a D-A moiety that itself is not TADF. The sensitizer-free OLEDs with DtCzBN-CNBT2 achieve a record-high maximum external quantum efficiency (EQE max ) of 40.2% and showed milder efficiency roll-off (EQE 1000 of 20.7%) compared to the DtCzBN-CNBT1-based devices (EQE max of 37.1% and EQE 1000 of 11.9%)., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Creating (room temperature) liquid crystalline TADF materials that retain the photophysical properties of the monomolecular TADF emitters remains a formidable challenge. The strong intramolecular interactions required for formation of a liquid crystal usually adversely affect the photophysical properties and balancing them is not yet possible. In this work, we present a novel host-guest approach enabling unperturbed, narrowband emission from an MR-TADF emissive core from strongly aggregated columnar hexagonal (Col h ) liquid crystals. By modifying the DOBNA scaffold with mesogenic groups bearing alkoxy chains of different lengths, we created a library of Col h liquid crystals featuring phase ranges >100 K and room temperature mesomorphism. Expectedly, these exhibit broad excimer emission from their neat films, so we exploited their high singlet (S 1 ∼2.9 eV) and triplet (T 1 ∼2.5 eV) energies by doping them with the MR-TADF guest BCzBN. Upon excitation of the host, efficient Förster Resonance Energy Transfer (FRET) resulted in almost exclusive emission from BCzBN. The ability of the liquid crystallinity of the host to not be adversely affected by the presence of BCzBN is demonstrated as is the localization of the guest molecules within the aliphatic chain network of the host, resulting in extremely narrowband emission (FWHM = 14-15 nm). With this work we demonstrate a strategy for the self-assembly of materials with previously mutually incompatible properties in emissive liquid crystalline systems: strong aggregation in Col h mesophases, and narrowband emission from a MR-TADF core., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A series of fluorescent carbazole-coumarins exhibiting good photoluminescence quantum yields and thermally activated delayed fluorescence (TADF) properties have been designed and synthetized using computer-aided density functional theory calculations. The TADF characteristics of the carbazole-coumarins were systematically explored both in solution and in the solid state, utilizing poly(methyl methacrylate) (PMMA) as a matrix. The study revealed that the introduction of carbazole units onto the coumarin benzene ring led to compounds with thermally induced reverse intersystem crossing and delayed fluorescence. The study further demonstrated the potential utility of these compounds in practical applications by incorporating them into a Cmr-PMMA-based sensor for molecular oxygen detection. The resulting sensor exhibited promising performance, highlighting the adaptability and efficacy of the synthesized TADF-carbazole-coumarin compounds for reversible molecular oxygen sensing., (© 2024 Wiley-VCH GmbH.)

Chiral multiresonant thermally activated delayed fluorescence (MR-TADF) materials show great potential as emitters in circularly polarized (CP) organic light-emitting diodes (CP-OLEDs) owing to their bright and narrowband CP emission. Here, two new chiral MR-TADF emitters t BuPh-BN and DPA- t BuPh-BN possessing intrinsically helical chirality have been synthesized and studied. The large steric interactions between the tert -butylphenyl groups not only induce the helical chirality but also provide a notable configurational stability to the enantiomers. Racemic mixtures of t BuPh-BN and DPA- t BuPh-BN show narrowband emission at 490 and 477 nm with full-width at half maximum (FWHM) of 25 and 28 nm and photoluminescence quantum yields, Φ PL , of 85 and 54% in toluene. The separated enantiomers of t BuPh-BN show symmetric circularly polarized luminescence (CPL) with respective dissymmetry factors | t | values of 1.5 × 10 g PL | values of 1.5 × 10 -3 and 0.9 × 10 -3 . The hyperfluorescence organic light-emitting diodes (HF-OLEDs) with t BuPh-BN and DPA- t BuPh-BN acting as terminal emitters and 2,3,4,5,6-penta-(9 H -carbazol-9-yl)benzonitrile (5CzBN) as their assistant dopant exhibited, respectively, maximum external quantum efficiencies (EQE max ) of 20.9 and 15.9% at 492 and 480 nm with FWHM of 34 and 38 nm. This work demonstrates a strategy for developing intrinsically helically chiral MR-TADF emitters possessing significant configurational stability, which can be used in HF-OLEDs., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Dual emission from thermally activated delayed fluorescence (TADF) emitters is often difficult to observe, especially in solution, limited by Kasha's rule. Two TADF dendrimers containing N-doped polycyclic aromatic hydrocarbons as acceptors are designed and synthesized. Compound 2GCzBPN, having a strongly twisted geometry, exhibits TADF, while 2GCzBPPZ, possessing a less twisted geometry, shows dual emission associated with the monomer and aggregate that is TADF. The demonstration reveals that 2GCzBPPZ can serve as a temperature sensor with excellent temperature sensitivity and remarkably wide emission color response in solution. By embedding 2GCzBPPZ in paraffin we demonstrate a spatial-temperature sensor that shows a noticeable emission shift from yellow to green and ultimately to blue as the temperature increases from 20 to 200 °C. We finally demonstrate the utility of these TADF dendrimers in solution-processed organic light-emitting diodes., (© 2024. The Author(s).)

Thermally activated delayed fluorescence (TADF) compounds are highly attractive as sensitizing and emitting materials for organic light-emitting diodes (OLEDs). The efficiency of the OLED depends on multiple parameters, most of which rely on the properties of the emitter including those that govern the internal quantum and outcoupling efficiencies. Herein, we investigate a series of aryl substituted acridine donor derivatives of the donor-acceptor TADF emitter DMAC-TRZ , with the objective of correlating their properties, such as triplet harvesting efficiency and transition dipole moment orientation, with their corresponding device efficiency. The decoration of the DMAC donor with substituted aryl groups not only modifies the molecular weight and length of the emitter but also affects the emission color and the capacity for the emitters to efficiently harvest triplet excitons. The presence of electron-withdrawing 4-cyanophenyl and 4-trifluoromethylphenyl groups in, respectively, CNPh-DMAC-TRZ and CF3Ph-DMAC-TRZ , blue-shifts the emission spectrum but slows down the reverse intersystem crossing rate constant ( k RISC ), while the opposite occurs in the presence of electron-donating groups in t BuPh-DMAC-TRZ and OMePh-DMAC-TRZ (red-shifted emission spectrum and faster k RISC ). In contrast to our expectations, the OLED performance of the five DMAC-TRZ derivatives does not scale with their degree of horizontal emitter orientation but follows the k RISC rates. This, in turn, demonstrates that triplet harvesting (and not horizontal emitter orientation) is the dominant effect for device efficiency using this family of emitters. Nonetheless, highly efficient OLEDs were fabricated with t BuPh-DMAC-TRZ and OMePh-DMAC-TRZ as emitters, with improved EQE max (∼28%) compared to the reference DMAC-TRZ devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Two novel deep-blue multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters, 1B-CzCrs and 2B-CzCrs, containing a fused carbazole unit were synthesized. The carbazole contributed to the emergence of TADF in these small molecules. Particularly, organic light-emitting diodes with 1B-CzCrs doped in the mCP host achieve a maximum external quantum efficiency of 12.8% at CIE coordinates of (0.146, 0.062).

We report square planar mononuclear Pt(II)-complexes of terpyridines in the form of [PtCl( L1 / L2 )]PF 6 as phosphorescent emitters (where L1 = 4-(3-pyridine)2,2':6',2''-terpyridine and L2 = 4'-(3-pyridinyl)-4,4''-di( tert -butyl)-2,2':6'2''-terpyridine). Complex 2 showed emission at 534 nm in the DCM solution with photoluminescence quantum efficiency (Φ PL ) = 14%, while in the mCBP host (5-wt % doped), the emission shifted to 584 nm with Φ PL = 37.8% and a phosphorescence lifetime (τ phos ) of 37.8 μs. Complex 2 in mCBP was used to fabricate a solution-processed phosphorescent organic light-emitting diode (PhOLED) which showed maximum external quantum efficiency (EQE max ) = 7.4% with yellow emission at λ EL = 570 nm and exhibited a low efficiency roll-off with an EQE drop to 7.0% at 1000 cd/m 2 .

Organic light-emitting diodes (OLEDs) that are able to emit high levels of circularly polarized (CP) light hold significant promise in numerous future technologies. Such devices require chiral emissive materials to enable CP electroluminescence. However, the vast majority of current OLED emitter classes, including the state-of-the-art triplet-harvesting thermally activated delayed fluorescence (TADF) materials, produce very low levels of CP electroluminescence. Here a host-guest strategy that allows for energy transfer between a chiral polymer host and a representative chiral TADF emitter is showcased. Such a mechanism results in a large amplification of the circular polarization of the emitter. As such, this study presents a promising avenue to further boost the performance of circularly polarized organic light-emitting diode devices, enabling their further development and eventual commercialization., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

We report a family of donor-acceptor thermally activated delayed fluorescent (TADF) compounds based on derivatives of DMAC-TRZ, that are strongly photoreducing. Both E ox and thus E* ox could be tuned via substitution of the DMAC donor with a Hammett series of p-substituted phenyl moieties while E red remained effectively constant. These compounds were assessed in the photoinduced dehalogenation of aryl halides, and analogues bearing electron withdrawing groups were found to produce the highest yields. Substrates of up to E red =-2.72 V could be dehalogenated at low PC loading (1 mol %) and under air, conditions much milder than previously reported for this reaction. Spectroscopic and chemical studies demonstrate that all PCs, including literature reference PCs, photodegrade, and that it is these photodegradation products that are responsible for the reactivity., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Narrowband emissive multiresonant thermally activated delayed fluorescence (MR-TADF) emitters are a promising solution to achieve the current industry-targeted color standard, Rec. BT.2020-2, for blue color without using optical filters, aiming for high-efficiency organic light-emitting diodes (OLEDs). However, their long triplet lifetimes, largely affected by their slow reverse intersystem crossing rates, adversely affect device stability. In this study, a helical MR-TADF emitter (f-DOABNA) is designed and synthesized. Owing to its π-delocalized structure, f-DOABNA possesses a small singlet-triplet gap, ΔE ST , and displays simultaneously an exceptionally faster reverse intersystem crossing rate constant, k RISC , of up to 2 × 10 6 s -1 and a very high photoluminescence quantum yield, Φ PL , of over 90% in both solution and doped films. The OLED with f-DOABNA as the emitter achieved a narrow deep-blue emission at 445 nm (full width at half-maximum of 24 nm) associated with Commission Internationale de l'Éclairage (CIE) coordinates of (0.150, 0.041), and showed a high maximum external quantum efficiency, EQE max , of ≈20%., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

α-Phenylthioaldehydes are readily prepared using a simple multi-step procedure and herein are introduced as a new precursor for the NHC-catalysed generation of acyl azolium and azolium enolate intermediates that are of widespread synthetic interest and utility. Treatment of α-phenylthioaldehydes with an NHC precatalyst and base produces an efficient redox rearrangement via a Breslow intermediate, elimination of thiophenolate, and subsequent rebound addition to the generated acyl azolium to give the corresponding thiol ester. In the presence of an external alcohol, competition between redox rearrangement and redox esterification can be controlled through judicious choice of the N -aryl substituent within the NHC precatalyst and the base used in the reaction. With NEt 3 as base, NHCs bearing electron-withdrawing ( N -C 6 F 5 or N -C 6 H 2 Cl 3 ) substituents favour redox rearrangement, while triazolium precatalysts with electron-rich N -aryl substituents ( N -Ph, N -Mes) result in preferential redox esterification. Using DBU, redox esterification is preferred due to transesterification of the initially formed thiol ester product. Additionally, α-phenylthioaldehyde-derived azolium enolates have been used in enantioselective formal [4 + 2]-cycloaddition reactions to access dihydropyridinone heterocycles with high enantioselectivity (up to >95 : 5 dr, 98 : 2 er)., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Modification of an unsymmetric B,O,N-doped aromatic core with peripheral mesogenic units triggers self-assembly into a columnar hexagonal mesophase, which is stable between 22 and 144 °C. The columnar assembly is preserved in a glassy state below 22 °C. The B,O,N-doped mesogen displays narrowband sky-blue multiresonance thermally activated delayed fluorescence (MR-TADF) under diluted conditions and bright excimer emission in condensed phase. Our combined experimental and theoretical approach provides insight into the development of strongly aggregating liquid crystalline MR-TADF emitters.

This proof-of-concept study cements the viability and generality of mechanophotocatalysis, merging mechanochemistry and photocatalysis to enable solvent-minimized photocatalytic reactions. We demonstrate the transmutation of four archetypal solution-state photocatalysis reactions to a solvent-minimized environment driven by the combined actions of milling, light, and photocatalysts. The chlorosulfonylation of alkenes and the pinacol coupling of aldehydes and ketones were conducted under solvent-free conditions with competitive or superior efficiencies to their solution-state analogues. Furthermore, decarboxylative alkylations are shown to function efficiently under solvent-minimized conditions, while the photoinduced energy transfer promoted [2+2] cycloaddition of chalcone experiences a significant initial rate enhancement over its solution-state variant. This work serves as a platform for future discoveries in an underexplored field: validating that solvent-minimized photocatalysis is not only generalizable and competitive with solution-state photocatalysis, but can also offer valuable advantages., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Organic light-emitting diodes (OLEDs) are a revolutionary light-emitting display technology that has been successfully commercialized in mobile phones and televisions 1,2 . The injected charges form both singlet and triplet excitons, and for high efficiency it is important to enable triplets as well as singlets to emit light. At present, materials that harvest triplets by thermally activated delayed fluorescence (TADF) are a very active field of research as an alternative to phosphorescent emitters that usually use heavy metal atoms 3,4 . Although excellent progress has been made, in most TADF OLEDs there is a severe decrease of efficiency as the drive current is increased, known as efficiency roll-off. So far, much of the literature suggests that efficiency roll-off should be reduced by minimizing the energy difference between singlet and triplet excited states (ΔE ST ) to maximize the rate of conversion of triplets to singlets by means of reverse intersystem crossing (k RISC ) 5-20 . We analyse the efficiency roll-off in a wide range of TADF OLEDs and find that neither of these parameters fully accounts for the reported efficiency roll-off. By considering the dynamic equilibrium between singlets and triplets in TADF materials, we propose a figure of merit for materials design to reduce efficiency roll-off and discuss its correlation with reported data of TADF OLEDs. Our new figure of merit will guide the design and development of TADF materials that can reduce efficiency roll-off. It will help improve the efficiency of TADF OLEDs at realistic display operating conditions and expand the use of TADF materials to applications that require high brightness, such as lighting, augmented reality and lasing., (© 2024. The Author(s).)

Herein, we report a fluorene-bridged double carbonyl/amine-based MR TADF emitter DDiKTa-F, formed by locking the conformation of the previously reported compound DDiKTa. Using this strategy, DDiKTa-F exhibited narrower, brighter, and red-shifted emission. The OLEDs with DDiKTa-F emitted at 493 nm and showed an EQE max of 15.3% with an efficiency roll-off of 35% at 100 cd m -2 .

In contemporary drug discovery, enhancing the sp 3 -hybridized character of molecular structures is paramount, necessitating innovative synthetic methods. Herein, we introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation. This approach serves as a versatile, metal-free C(sp 3 )-C(sp 3 ) cross-coupling platform. We demonstrate its synthetic value as a safer, broadly applicable C1 homologation of carboxylic acids, offering an alternative to the traditional Arndt-Eistert reaction. Additionally, our method provides direct access to cyclic and acyclic β-arylethylamines using diverse aldehyde-derived sulfonyl hydrazones. Notably, the methodology proves to be compatible with the late-stage functionalization of peptides on solid-phase, streamlining the modification of intricate peptides without the need for exhaustive de-novo synthesis., (© 2024. The Author(s).)

Herein, we show that there is significant variation in both the triplet energies and redox properties of photocatalysts as a function of solvent based on a study of eight PCs in four solvents of varying polarity. A range of photocatalytic electron and energy transfer reactions were investigated using a subset of the PCs. For the photoredox reactions, the yields are not correlated with solvent polarity. Instead, when the PC could promote the formation of the target product, we observed photodegradation for all PCs across all solvents, something that is rarely investigated in the literature. This, therefore, makes it difficult to ascertain whether the parent PC and/or the photodegraded product is responsible for the photochemistry, or indeed, whether photodegradation is actually detrimental to the reaction yield. Conversely, the PCs were found to be photostable for energy transfer reactions; however, yields were not correlated to the triplet energies of the PCs, highlighting that triplet energies alone are not a suitable descriptor to discriminate the performance between PCs in photoinduced energy transfer processes., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

OLED technology has revolutionized the display industry and is promising for lighting. Despite its maturity, there remain outstanding device and materials challenges to address. Particularly, achieving stable and highly efficient blue OLEDs is still proving to be difficult; the vast array of degradation mechanisms at play, coupled with the precise balance of device parameters needed for blue high-performance OLEDs, creates a unique set of challenges in the quest for a suitably stable yet high-performance device. Here, we discuss recent progress in the understanding of device degradation pathways and provide an overview of possible strategies to increase device lifetimes without a significant efficiency trade-off. Only careful consideration of all variables that go into OLED development, from the choice of materials to a deep understanding of which degradation mechanisms need to be suppressed for the particular structure, can lead to a meaningful positive change toward commercializable blue devices.

In this study, we explore the impact of halogen functionalization on the photophysical properties of the commonly used organic light-emitting diode (OLED) host material, 1,3-bis( N -carbazolyl)benzene (mCP). Derivatives with different numbers and types of halogen substituents on mCP were synthesized. By measuring steady-state and transient photoluminescence at 6 K, we study the impact of the type, number, and position of the halogens on the intersystem crossing and phosphorescence rates of the compounds. In particular, the functionalization of mCP with 5 bromine atoms results in a significant increase of the intersystem crossing rate by a factor of 300 to a value of (1.5 ± 0.1) × 10 10 s -1 , and the phosphorescence rate increases by 2 orders of magnitude. We find that the singlet radiative decay rate is not significantly modified in any of the studied compounds. In the second part of the paper, we describe the influence of these compounds on the reverse intersystem crossing of the 7,10-bis(4-(diphenylamino)phenyl)-2,3-dicyanopyrazino-phenanthrene (TPA-DCPP), a TADF guest, via the external heavy atom effect. Their use results in an increase of the reverse intersystem crossing (RISC) rate from (8.1 ± 0.8) × 10 3 s -1 for mCP to (2.7 ± 0.1) × 10 4 s -1 for mCP with 5 bromine atoms. The effect is even more pronounced for the mCP analogue containing a single iodine atom, which gives a RISC rate of (3.3 ± 0.1) × 10 4 s -1 . Time-dependent DFT calculations reveal the importance of the use of long-range corrected functionals to predict the effect of halogenation on the optical properties of the mCP, and the relativistic approximation (ZORA) is used to provide insight into the strength of the spin-orbit coupling matrix element between the lowest-lying excited singlet and triplet states in the different mCP compounds., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Given the current interest in materials containing 1,4-azaborine units, the development of new routes to these structures is important. Carbonyl directed electrophilic borylation using BBr 3 is a facile method for the ortho -borylation of N , N -diaryl-amide derivatives. Subsequent addition of Et 3 SiH results in carbonyl reduction and then formation of 1,4-azaborines that can be protected in situ using a Grignard reagent. Overall, borylation-reduction-borylation is a one-pot methodology to access 1,4-azaborines from simple precursors.

Organic small molecules exhibiting both thermally activated delayed fluorescence (TADF) and wide-ranging piezochromism (Δ λ > 150 nm) in the near-infrared region have rarely been reported in the literature. We present three emitters MeTPA-BQ, tBuTPA-BQ and TPPA-BQ based on a hybrid acceptor, benzo[g]quinoxaline-5,10-dione, that emit via TADF, having photoluminescence quantum yields, Φ PL , of 39-42% at photoluminescence (PL) maxima, λ PL , of 625-670 nm in 2 wt% doped films in 4,4'-bis( N -carbazolyl)-1,1'-biphenyl (CBP). Despite their similar chemical structures, the PL properties in the crystalline states of MeTPA-BQ ( λ em = 735 nm, Φ PL = 2%) and tBuTPA-BQ ( λ em = 657 nm, Φ PL = 11%) are significantly different. Further, compounds tBuTPA-BQ and TPPA-BQ showed a significant PL shift of ∼98 and ∼165 nm upon grinding of the crystalline samples, respectively. Deep-red organic light-emitting diodes with MeTPA-BQ and tBuTPA-BQ were also fabricated, which showed maximum external quantum efficiencies, EQE max , of 10.1% ( λ EL = 650 nm) and 8.5% ( λ EL = 670 nm), respectively., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Corannulene-derived materials have been extensively explored in energy storage and solar cells, however, are rarely documented as emitters in light-emitting sensors and organic light-emitting diodes (OLEDs), due to low exciton utilization. Here, we report a family of multi-donor and acceptor (multi-D-A) motifs, TCzPhCor, TDMACPhCor, and TPXZPhCor, using corannulene as the acceptor and carbazole (Cz), 9,10-dihydro-9,10-dimethylacridine (DMAC), and phenoxazine (PXZ) as the donor, respectively. By decorating corannulene with different donors, multiple phosphorescence is realized. Theoretical and photophysical investigations reveal that TCzPhCor shows room-temperature phosphorescence (RTP) from the lowest-lying T 1 ; however, for TDMACPhCor, dual RTP originating from a higher-lying T 1 (T 1 H ) and a lower-lying T 1 (T 1 L ) can be observed, while for TPXZPhCor, T 1 H -dominated RTP occurs resulting from a stabilized high-energy T 1 geometry. Benefiting from the high-temperature sensitivity of TPXZPhCor, high color-resolution temperature sensing is achieved. Besides, due to degenerate S 1 and T 1 H states of TPXZPhCor, the first corannulene-based solution-processed afterglow OLEDs is investigated. The afterglow OLED with TPXZPhCor shows a maximum external quantum efficiency (EQE max ) and a luminance (L max ) of 3.3 % and 5167 cd m -2 , respectively, which is one of the most efficient afterglow RTP OLEDs reported to date., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Electrochemiluminescence (ECL) is a rapidly growing discipline with many analytical applications from immunoassays to single-molecule detection. At the forefront of ECL research is materials chemistry, which looks at engineering new materials and compounds exhibiting enhanced ECL efficiencies compared to conventional fluorescent materials. In this review, we summarize recent molecular design strategies that lead to high efficiency ECL. In particular, we feature recent advances in the use of thermally activated delayed fluorescence (TADF) emitters to produce enhanced electrochemiluminescence. We also document how hydrogen bonding, aggregation, and crystallization can each be recruited in the design of materials showing enhanced electrochemiluminescence., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The development of materials that emit in the deep-red to near-infrared region of the spectrum has attracted significant attention due to their potential as optical sensing and imaging reagents in biology. Herein, we report the synthesis and optoelectronic characterization of four anthraquinone-based emitters, T-tBuCz-AQ , T-MeOCz-AQ , C-tBuCz-AQ , and C-MeOCz-AQ , and two pyrazoloanthrone-based emitters, tBuCz-PA and DMAC-PA . Depending on the donor, these compounds emit in the spectral range between 640 and 750 nm in the neat film, while the emission of the 10 wt% doped films in poly(methyl methacrylate) (PMMA) is blue-shifted between 600 and 700 nm and has low photoluminescence quantum yields between 2.6% and 6.6%. Of these compounds, T-tBuCz-AQ , T-MeOCz-AQ , and C-tBuCz-AQ exhibited thermally activated delayed fluorescence (TADF) in 10 wt% doped films in PMMA, while the crystals of T-tBuCz-AQ also showed TADF. Compound tBuCz-PA showed a high-contrast and reversible photoluminescence (PL) response upon mechanical grinding and hexane fuming., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Sudhakar, Slawin and Zysman-Colman.)

Bromo-functionalized B 1 -polycyclic aromatic hydrocarbons (PAHs) with LUMOs of less than -3.0 eV were synthesized and used in cross-couplings to form donor-acceptor materials. These materials spanned a range of S 1 energies, with a number showing thermally activated delayed fluorescence and significant emission in the near-infrared region of the spectrum. These B 1 -PAHs represent a useful family of acceptors that can be readily synthesized and functionalized.

Two multiresonant thermally activated delayed fluorescence (MR-TADF) emitters are presented and it is shown how further borylation of a deep-blue MR-TADF emitter, DIDOBNA-N, both blueshifts and narrows the emission producing a new near-UV MR-TADF emitter, MesB-DIDOBNA-N, are shown. DIDOBNA-N emits bright blue light (Φ PL = 444 nm, FWHM = 64 nm, Φ PL = 81%, τ d = 23 ms, 1.5 wt% in TSPO1). The deep-blue organic light-emitting diode (OLED) based on this twisted MR-TADF compound shows a very high maximum external quantum efficiency (EQE max ) of 15.3% for a device with CIE y of 0.073. The fused planar MR-TADF emitter, MesB-DIDOBNA-N shows efficient and narrowband near-UV emission (λ PL = 402 nm, FWHM = 19 nm, Φ PL = 74.7%, τ d = 133 ms, 1.5 wt% in TSPO1). The best OLED with MesB-DIDOBNA-N, doped in a co-host, shows the highest efficiency reported for a near-UV OLED at 16.2%. With a CIE y coordinate of 0.049, this device also shows the bluest EL reported for a MR-TADF OLED to date., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Multiresonant thermally activated delayed fluorescence (MR-TADF) compounds are attractive as emitters for organic light-emitting diodes (OLEDs) as they can simultaneously harvest both singlet and triplet excitons to produce light in the device and show very narrow emission spectra, which translates to excellent color purity. Here, we report the first example of an MR-TADF emitter (DOBDiKTa) that fuses together fragments from the two major classes of MR-TADF compounds, those containing boron (DOBNA) and those containing carbonyl groups (DiKTa) as acceptor fragments in the MR-TADF skeleton. The resulting molecular design, this compound shows desirable narrowband pure blue emission and efficient TADF character. The co-host OLED with DOBDiKTa as the emitter showed a maximum external quantum efficiency (EQE max ) of 17.4 %, an efficiency roll-off of 32 % at 100 cd m -2 , and Commission Internationale de l'Éclairage (CIE) coordinates of (0.14, 0.12). Compared to DOBNA and DiKTa, DOBDiKTa shows higher device efficiency with reduced efficiency roll-off while maintaining a high color purity, which demonstrates the promise of the proposed molecular design., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The importance of intermediate triplet states and the nature of excited states has gained interest in recent years for the thermally activated delayed fluorescence (TADF) mechanism. It is widely accepted that simple conversion between charge transfer (CT) triplet and singlet excited states is too crude, and a more complex route involving higher-lying locally excited triplet excited states has to be invoked to witness the magnitude of the rate of reverse inter-system crossing (RISC) rates. The increased complexity has challenged the reliability of computational methods to accurately predict the relative energy between excited states as well as their nature. Here, we compare the results of widely used density functional theory (DFT) functionals, CAM-B3LYP, LC-ωPBE, LC-ω*PBE, LC-ω*HPBE, B3LYP, PBE0, and M06-2X, against a wavefunction-based reference method, Spin-Component Scaling second-order approximate Coupled Cluster (SCS-CC2), in 14 known TADF emitters possessing a diversity of chemical structures. Overall, the use of the Tamm-Dancoff Approximation (TDA) together with CAM-B3LYP, M06-2X, and the two ω-tuned range-separated functionals LC-ω*PBE and LC-ω*HPBE demonstrated the best agreement with SCS-CC2 calculations in predicting the absolute energy of the singlet S 1 , and triplet T 1 and T 2 excited states and their energy differences. However, consistently across the series and irrespective of the functional or the use of TDA, the nature of T 1 and T 2 is not as accurately captured as compared to S 1 . We also investigated the impact of the optimization of S 1 and T 1 excited states on Δ E ST and the nature of these states for three different functionals (PBE0, CAM-B3LYP, and M06-2X). We observed large changes in Δ E ST using CAM-B3LYP and PBE0 functionals associated with a large stabilization of T 1 with CAM-B3LYP and a large stabilization of S 1 with PBE0, while Δ E ST is much less affected considering the M06-2X functional. The nature of the S 1 state barely evolves after geometry optimization essentially because this state is CT by nature for the three functionals tested. However, the prediction of the T 1 nature is more problematic since these functionals for some compounds interpret the nature of T 1 very differently. SCS-CC2 calculations on top of the TDA-DFT optimized geometries lead to a large variation in terms of Δ E ST and the excited-state nature depending on the chosen functionals, further stressing the large dependence of the excited-state features on the excited-state geometries. The presented work highlights that despite good agreement of energies, the description of the exact nature of the triplet states should be undertaken with caution.

Extensive research has been devoted to the development of thermally activated delayed fluorescence emitters, especially those showing pure-blue emission for use in lighting and full-color display applications. Toward that goal, herein we report a novel weak donor, 1,4-azaborine (AZB), with complementary electronic and structural properties compared to the widely used dimethylacridan (DMAC) or carbazole (Cz) donors. Coupled with a triazine acceptor, AZB-Ph-TRZ is the direct structural analogue of the high-performance and well-studied green TADF emitter DMAC-TRZ and has Δ E ST = 0.39 eV, a photoluminescence quantum yield (Φ PL ) of 27%, and λ PL = 415 nm in 10 wt % doped mCP films. The shortened analogue AZB-TRZ possesses red-shifted emission with a reduced singlet-triplet gap (Δ E ST = 0.01 eV) and fast reverse intersystem crossing ( k RISC of 5 × 10 6 s -1 ) in mCP. Despite a moderate Φ PL of 34%, OLEDs with AZB-TRZ in mCP showed sky-blue emission with CIE 1931 ( x,y ) of (0.22,0.39) and a maximum external quantum efficiency (EQE max ) of 10.5%. Expanding the chemist's toolkit for the design of blue donor-acceptor TADF materials will enable yet further advances in the future, as AZB is paired with a wider range of acceptor groups.

Carbazolyl dicyanobenzene (CDCB) derivates exhibiting thermally activated delayed fluorescence (TADF) have shown themselves to be excellent photocatalysts over recent years, particularly 4CzIPN , although investigation into organic TADF compounds as photocatalysts outside of the CDCB group has been limited. Herein, we report an alternative donor-acceptor TADF structure, 9,9'-(sulfonylbis(pyrimidine-5,2-diyl))bis(3,6-di- tert -butyl-9H-carbazole), pDTCz-DPmS , for use as a photocatalyst (PC). A comparison of the electrochemical and photophysical properties of pDTCz-DPmS with 4CzIPN in a range of solvents identifies the former as a better ground state reducing agent and photoreductant, while both exhibit similar oxidation capabilities in the ground and excited state. The increased conjugation of pDTCz-DPmS relative to 4CzIPN presents a more intense CT band in the UV-vis absorption spectrum, aiding in the light absorption of this molecule. Prompt and delayed emission lifetimes are observed for pDTCz-DPmS , confirming the TADF nature, both of which are sufficiently long-lived to participate in productive photochemistry. These combined properties make pDTCz-DPmS useful in photocatalysis reactions, covering a range of photoredox oxidative and reductive quenching reactions, as well as those involving a dual Ni(II) cocatalyst, alongside energy transfer processes. The higher triplet energy and increased photostability of pDTCz-DPmS compared with 4CzIPN were found to be advantages of this organic PC.

The key intramolecular [2 + 2] photochemical cycloaddition step in the synthesis of dimethyl cubane-1,4-dicarboxylate is performed with substoichiometric amounts of the photosensitizer benzophenone. The reaction proceeds via a Dexter energy transfer process between the triplet excited state benzophenone and a well-known cubane precursor diene. The use of the cheap and widely available benzophenone as the photosensitizer enables lower energy light to be used than the traditional photochemical process.

The use of thermally activated delayed fluorescence (TADF) emitters and emitters that show preferential horizontal orientation of their transition dipole moment (TDM) are two emerging strategies to enhance the efficiency of OLEDs. We present the first example of a liquid crystalline multi-resonance TADF (MR-TADF) emitter, DiKTa-LC. The compound possesses a nematic liquid crystalline phase between 80 °C and 110 °C. Importantly, the TDM of the spin-coated film shows preferential horizontal orientation, with an anisotropy factor, a, of 0.28, which is preserved in doped poly(vinylcarbazole) films. Green-emitting (λ EL =492 nm) solution-processed OLEDs based on DiKTa-LC showed an EQE max of 13.6 %. We thus demonstrate for the first time how self-assembly of a liquid crystalline TADF emitter can lead to the so-far elusive control of the orientation of the transition dipole in solution-processed films, which will be of relevance for high-performance solution-processed OLEDs., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Charge diffusion and extraction are crucial steps in the operation of solar cells. Here we show that time-resolved photoluminescence can be used to study electron diffusion in hybrid perovskite films and subsequent transfer to the adjacent electron extraction layer. As diffusion and transfer to the extraction layer are consecutive processes, they can be hard to distinguish, but by exciting from each side of the sample we can separate them and identify which process limits charge extraction. We find that the introduction of a fullerene monolayer between the methylammonium lead iodide (MAPbI 3 ) and the electron-transporting SnO 2 layers greatly increases the electron transfer velocity between them to the extent that electron diffusion limits the rate of electron extraction. Our results suggest that increasing the electron diffusion coefficient in MAPbI 3 would further enhance the electron extraction rate, which could result in more efficient n-i-p type solar cells.

A key challenge in developing emissive materials for organic light-emitting diodes is to optimize their colour saturation, which means targeting narrowband emitters. In this combined theoretical and experimental study, we investigate the use of heavy atoms in the form of trimethylsilyl groups as a tool to reduce the intensity of the vibrations in the 2-phenylpyridinato ligands of emissive iridium(III) complexes that contribute to the vibrationally coupled modes that broaden the emission profile. An underutilised computational technique, Frank-Condon vibrationally coupled electronic spectral modelling, was used to identify the key vibrational modes that contribute to the broadening of the emission spectra in known benchmark green-emitting iridium(III) complexes. Based on these results, a family of eight new green-emitting iridium complexes containing trimethylsilyl groups substituted at different positions of the cyclometalating ligands has been prepared to explore the impact that these substituents have on reducing the intensity of the vibrations and the resulting reduction in the contribution of vibrationally coupled emission modes to the shape of the emission spectra. We have demonstrated that locating a trimethylsilyl group at the N4 or N5 position of the 2-phenylpyridine ligand damps the vibrational modes of the iridium complex and provides a modest narrowing of the emission spectrum of 8-9 nm (or 350 cm -1 ). The strong correlation between experimental and calculated emission spectra highlights the utility of this computational method to understand how the vibrational modes contribute to the profile of the emission spectra in phosphorescent iridium(III) emitters.

The development of efficient blue donor-acceptor thermally activated delayed fluorescence (TADF) emitters remains a challenge. To enhance the efficiency of TADF-related processes of the emitter, we targeted a molecular design that would introduce a large number of intermediate triplet states between the lowest energy excited triplet (T 1 ) and singlet (S 1 ) excited states. Here, we introduce an oligomer approach using repetitive donor-acceptor units to gradually increase the number of quasi-degenerate states. In our design, benzonitrile (BN) moieties were selected as acceptors that are connected together via the amine donors, acting as bridges to adjacent BN acceptors. To preserve the photoluminescence emission wavelength across the series, we employed a design based on an ortho substitution pattern of the donors about the BN acceptor that induces a highly twisted conformation of the emitters, limiting the conjugation. Via a systematic photophysical study, we show that increasing the oligomer size allows for enhancement of the intersystem crossing and reverse intersystem crossing rates. We attribute the increasing intersystem crossing rate to the increasing number of intermediate triplet states along the series, confirmed by the time-dependent density functional theory. Overall, we report an approach to enhance the efficiency of TADF-related processes without changing the blue photoluminescence color., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The electrochemistry, electrochemiluminescence (ECL), and chemiluminescence (CL) properties of a thermally activated delayed fluorescence (TADF) emitter 4,4'-(1,2-dihydroacenaphthylene-5,6-diyl)bis( N , N -diphenylaniline) (TPA-ace-TRZ) and three of its analogues were investigated. TPA-ace-TRZ exhibits both (a) delayed onset of ECL and (b) long-persistent luminescence, which we have attributed to the formation of an aggregate excited state in excimer or exciplex form. The evidence of this aggregate excited state was consistent across ECL annihilation and coreactant pathways as well as in CL. The absolute ECL efficiency of TPA-ace-TRZ using benzoyl peroxide (BPO) as a coreactant was found to be 0.028%, which was 9-fold stronger than the [Ru(bpy) 3 ] 2+ /BPO reference coereactant system. Furthermore, the absolute CL quantum efficiency of TPA-ace-TRZ was determined to be 0.92%. The performance and flexibility of the TADF emitter TPA-ace-TRZ under these various emissive pathways are highly desirable toward applications in sensing, imaging, and light-emitting devices.

Here, we explored the possibility of using cycloparaphenylenes (CPP) within a donor-acceptor TADF emitter design. 4PXZPh-[10]CPP contains four electron-donating moieties connected to a [10]CPP . In the 15 wt % doped in CzSi film, 4PXZPh-[10]CPP showed sky-blue emission with λ PL = 475 nm, Φ PL = 29%, and triexponential emission decays with τ PL of 4.4, 46.3, and 907.8 ns. Solution-processed OLEDs using 4PXZPh-[10]CPP exhibited sky-blue emission with an λ EL of 465 nm and an EQE max of 1.0%.

We present a p- and n-doped nonacene compound, NOBNacene, that represents a rare example of a linearly extended ladder-type multiresonant thermally activated delayed fluorescence (MR-TADF) emitter. This compound shows efficient narrow deep blue emission, with a λ PL of 410 nm, full width at half maximum, FWHM, of 38 nm, photoluminescence quantum yield, Φ PL of 71 %, and a delayed lifetime, τ d of 1.18 ms in 1.5 wt % TSPO1 thin film. The organic light-emitting diode (OLED) using this compound as the emitter shows a comparable electroluminescence spectrum peaked at 409 nm (FWHM=37 nm) and a maximum external quantum efficiency (EQE max ) of 8.5 % at Commission Internationale de l'Éclairage (CIE) coordinates of (0.173, 0.055). The EQE max values were increased to 11.2 % at 3 wt % doping of the emitter within the emissive layer of the device. At this concentration, the electroluminescence spectrum broadened slightly, leading to CIE coordinates of (0.176, 0.068)., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The design and regulation of multiple room-temperature phosphorescence (RTP) processes are formidably challenging due to the restrictions imposed by Kasha's rule. Here, we report a general design principle for materials that show multiple RTP processes, which is informed by our study of four compounds where there is modulation of the linker hybridization between donor (D) and acceptor (A) groups. Theoretical modeling and photophysical experiments demonstrate that multiple RTP processes can be achieved in sp 3 C-linked D-A compounds due to the arrest of intramolecular electronic communication between two triplet states (T 1 H and T 1 L ) localized on the donor and acceptor or between two triplet states, one localized on the donor and one delocalized across aggregated acceptors. However, for the sp 2 C-linked D-A counterparts, RTP from one locally excited T 1 state is observed because of enhanced excitonic coupling between the two triplet states of molecular subunits. Single-crystal and reduced density gradient analyses reveal the influence of molecular packing on the coincident phosphorescence processes and the origin of the observed aggregate phosphorescence. These findings provide insights into higher-lying triplet excited-state dynamics and into a fundamental design principle for designing compounds that show multiple RTP.

Donor-acceptor (D-A) thermally activated delayed fluorescent (TADF) compounds, such as 4CzIPN, have become a widely used sub-class of organic photocatalysts for a plethora of photocatalytic reactions. Multi-resonant TADF (MR-TADF) compounds, a subclass of TADF emitters that are rigid nanographene derivatives, such as DiKTa and Mes 3 DiKTa, have to date not been explored as photocatalysts. In this study both DiKTa and Mes 3 DiKTa were found to give comparable or better product yield than 4CzIPN in a range of photocatalytic processes that rely upon reductive quenching, oxidative quenching, energy transfer and dual photocatalytic processes. In a model oxidative quench process, DiKTa and Mes 3 DiKTa gave increased reaction rates in comparison to 4CzIPN, with DiKTa being of particular interest due to the lower material cost (£0.94/mmol) compared to that of 4CzIPN (£3.26/mmol). These results suggest that DiKTa and Mes 3 DiKTa would be excellent additions to any chemist's collection of photocatalysts., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Condensation of 2-vinylanilines and conjugated aldehydes followed by an efficient light-mediated cyclisation selectively yields either substituted tetrahydroquinolines with typically high dr, or in the presence of an iridium photocatalyst the synthesis of quinoline derivatives is demonstrated. These atom economical processes require mild conditions, with the substrate scope demonstrating excellent site selectivity and functional group tolerance, including azaarene-bearing substrates. A thorough experimental mechanistic investigation explores multiple pathways and the key role that imine and iminium intermediates play in the absorption of visible light to generate reactive excited states. The synthetic utility of the reactions is demonstrated on gram scale quantities in both batch and flow, alongside further manipulation of the medicinally relevant products., (© 2022 Wiley-VCH GmbH.)

Herein, we demonstrate how judicious selection of the donor decorating a central multi-resonant thermally activated delayed fluorescence (MR-TADF) core based on DiKTa can lead to very high-performance OLEDs. By decorating the DiKTa core with triphenylamine (TPA) and diphenylamine (DPA), 3TPA-DiKTa and 3DPA-DiKTa exhibit bright, narrowband green and red emission in doped films, respectively. The OLEDs based on these emitters showed record-high performance for this family of emitters with maximum external quantum efficiencies (EQE max ) of 30.8 % for 3TPA-DiKTa at λ EL of 551 nm and 16.7 % for 3DPA-DiKTa at λ EL =613 nm. The efficiency roll-off in the OLEDs was improved significantly by using 4CzIPN as an assistant dopant in hyperfluorescence (HF) devices. The outstanding device performance has been attributed to preferential horizontal orientation of the transition dipole moments of 3TPA-DiKTa and 3DPA-DiKTa., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The use of the recently reported organic multi-resonant thermally activated delayed fluorescence (MR-TADF) photocatalyst DiKTa allows for the modular synthesis of 1,4-diketones under mild and metal-free conditions. The reaction proceeds via a three-component relay process in the presence of an N-heterocyclic carbene (NHC) organocatalyst.

We designed and synthesized two new ionic thermally activated delayed fluorescent (TADF) emitters that are charged analogues of a known multiresonant TADF (MR-TADF) compound, DiKTa . The emission of the charged derivatives is red-shifted compared to the parent compound. For instance, DiKTa-OBuIm emits in the green (λ PL = 499 nm, 1 wt % in mCP) while DiKTa-DPA-OBuIm emits in the red (λ PL = 577 nm, 1 wt % in mCP). In 1 wt % mCP films, both emitters showed good photoluminescence quantum yields of 71% and 61%, and delayed lifetimes of 316.6 μs and 241.7 μs, respectively, for DiKTa-OBuIm and DiKTa-DPA-OBuIm , leading to reverse intersystem crossing rates of 2.85 × 10 3 s -1 and 3.04 × 10 3 s -1 . Light-emitting electrochemical cells were prepared using both DiKTa-OBuIm and DiKTa-DPA-OBuIm as active emitters showing green (λ max = 534 nm) and red (λ max = 656 nm) emission, respectively., (Copyright © 2022, Karaman et al.)

Two new deep-blue narrowband multi-resonant emitters, 1B-DTACrs and 2B-DTACrs, one of which shows thermally activated delayed fluorescence (TADF), based on boron, nitrogen, and oxygen doped nanographenes are reported. Devices based on 2B-DTACrs showed an EQE max of 14.8% and CIE coordinates of (0.150, 0.044), which are very close to the BT.2020 requirement for blue pixels.

Room-temperature phosphorescence (RTP) originating from higher-lying triplet excitons remains a rather rarely documented occurrence for purely organic molecular systems. Here, we report two naphthalene-based RTP luminophores whose phosphorescence emission is enabled by radiative decay of high-lying triplet excitons. In contrast, upon cooling the dominant phosphorescence originates from the lowest-lying triplet excited state, which is manifested by a red-shifted emission. Photophysical and theoretical studies reveal that the unusual RTP results from thermally activated excitonic coupling between different conformations of the compounds. Aggregation-regulated excitonic coupling is observed when increasing the doping concentration of the emitters in poly(methylmethacrylate) (PMMA). Further, the RTP quantum efficiency improves more than 80-fold in 1,3-bis(N-carbazolyl)benzene (mCP) compared to that in PMMA. This design principle offers important insight into triplet excited state dynamics and has been exploited in afterglow-indicating temperature sensing., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)