Development of an Organic Emitter Exhibiting Reverse Intersystem Crossing Faster than Intersystem Crossing.

In thermally activated delayed fluorescence (TADF)-based organic light-emitting diodes (OLEDs), acceleration of reverse intersystem crossing (RISC) and suppression of intersystem crossing (ISC) are demanded to shorten a lifetime of triplet excitons. As a system realizing RISC faster than ISC, inverted singlet-triplet excited states (iST) with a negative energy difference (ΔEST) between the lowest excited singlet and the lowest triplet states have been gathering much attention recently. Here, we have focused on an asymmetric hexa-azaphenalene (A6AP) core to obtain a new insight into iST. Based on A6AP, we have newly designed A6AP-Cz with the calculated ΔEST of -44 meV. The experimental studies of a synthesized A6AP-Cz revealed that the lifetime of delayed fluorescence (τDF) was only 54 ns, which was the shortest among all organic materials. The rate constant of RISC (kRISC=1.9×107 s-1) was greater than that of ISC (kISC=1.0×107 s-1). The negative ΔEST of A6AP-Cz was experimentally confirmed from 1) the kRISC and kISC (-45 meV) and 2) the temperature-dependent τDF. 3) The onsets of fluorescence and phosphorescence spectra at 77 K also supported the evidence of negative ΔEST (-73 meV). This study demonstrated the potential of A6AP as an iST core for the first time.

Promoting Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence via the Heavy-Atom Effect.

Thermally activated delayed fluorescence (TADF) molecules are promising for realizing durable organic light-emitting diodes in all color regions. Fast reverse intersystem crossing (RISC) is a way of improving the device lifetime of TADF-based organic light-emitting diodes. To date, RISC rate constants (kRISC) of 108 s-1 have been reported for metal-free TADF molecules. Here, we report the heavy-atom effect on TADF and a molecular design for further promoting RISC. First, we reproduced all the relevant rate constants of a sulfur-containing TADF molecule (with kRISC of 108 s-1) via density functional theory. The role of the heavy-atom effect on the rapid RISC process was clarified. Our calculations also predicted that much larger kRISC (>1010 s-1) will be obtained for selenium- and tellurium-containing TADF molecules. However, a polonium-containing molecule promotes phosphorescence without exhibiting TADF, indicating that a too strong heavy-atom effect is unfavorable for achieving both rapid RISC and efficient TADF.

Theoretical Determination of Rate Constants from Excited States: Application to Benzophenone.

A cost-effective method of theoretically predicting electronic-transition rate constants from the excited states of molecules is reported. This method is based on density functional theory calculations of electronic states and quantitative rate constant determination with the Fermi golden rule. The method is applied to the theoretical determination of the excited-state decay mechanism of photoexcited benzophenone, a representative molecule in photochemistry and biochemistry. Calculated rate constants for benzophenone are quantitatively consistent with experimental ones, which validates the reliability of our rate constant calculation. The calculated population kinetics indicate that S1 → T2 → T1 → S0 is the predominant decay pathway.

Molecular Vibration Accelerates Charge Transfer Emission in a Highly Twisted Blue Thermally Activated Delayed Fluorescence Material.

In the development of new organic light-emitting diodes, thermally activated delayed fluorescence (TADF) materials have drawn interest because of their ability to upconvert electrically generated triplet excitons into singlets. Efficient TADF requires a well-balanced large transition dipole moment (µ) between the lowest excited singlet state (S1) and the ground state (S0) and a small energy splitting (ΔEST) between S1 and the lowest triplet state (T1). However, a number of highly twisted donor-acceptor-type TADF molecules have been reported to exhibit high performance in OLEDs, although these molecules may sacrifice µ in exchange for a very small ΔEST. Here, we theoretically investigate the origin of efficient emission from a perpendicularly twisted blue emitter, MA-TA. In this system, the µ value almost vanishes in the static approximation; however, vibrational contributions increase µ considerably. Hence, we show that the dynamics of excitons have a critical role in such TADF systems.

Effect of Vibronic Coupling on Correlated Triplet Pair Formation in the Singlet Fission Process of Linked Tetracene Dimers.

Tetracene-based singlet fission (SF) materials show application prospects as triplet sensitizers in organic optoelectronics. SF involves internal conversion from photoexcited singlet states 1(S1S0) to correlated triplet pair states 1(T1T1). We derive an expression for the internal conversion rate on the basis of the Fermi golden rule with an artificial Lorentzian broadening. The internal conversion rate depends on the interstate vibronic couplings (VCs) and energy difference (ΔESF) between 1(S1S0) and 1(T1T1). Therefore, understanding the interplay between interstate VCs and ΔESF is necessary to reveal how the structure-property relationship affects the SF efficiency. Here, we propose a method to quantitatively analyze interstate VCs between 1(S1S0) and 1(T1T1). We apply this method to SF in ortho-, meta-, and para-bis(ethynyltetracenyl)benzene and identify an effect of interstate VCs on the 1(T1T1) formation rate. The interstate VCs of the meta dimer are remarkably weak, which reasonably explains the experimentally obtained slow 1(T1T1) formation rate. The weak VCs result from a very small overlap density between 1(S1S0) and 1(T1T1) of the meta dimer. Furthermore, we investigate structure-dependence of the 1(T1T1) formation rate of the para dimer and find that the para dimer shows large VCs and small ΔESF when the rotational angle between the two tetracene units is large, which leads to the faster 1(T1T1) formation rate than those of the ortho and meta dimers. The rotation of the tetracene units is the origin of the experimentally observed fast 1(T1T1) formation rate of the para dimer.

Highly efficient organic light-emitting diodes from delayed fluorescence.

The inherent flexibility afforded by molecular design has accelerated the development of a wide variety of organic semiconductors over the past two decades. In particular, great advances have been made in the development of materials for organic light-emitting diodes (OLEDs), from early devices based on fluorescent molecules to those using phosphorescent molecules. In OLEDs, electrically injected charge carriers recombine to form singlet and triplet excitons in a 1:3 ratio; the use of phosphorescent metal-organic complexes exploits the normally non-radiative triplet excitons and so enhances the overall electroluminescence efficiency. Here we report a class of metal-free organic electroluminescent molecules in which the energy gap between the singlet and triplet excited states is minimized by design, thereby promoting highly efficient spin up-conversion from non-radiative triplet states to radiative singlet states while maintaining high radiative decay rates, of more than 10(6) decays per second. In other words, these molecules harness both singlet and triplet excitons for light emission through fluorescence decay channels, leading to an intrinsic fluorescence efficiency in excess of 90 per cent and a very high external electroluminescence efficiency, of more than 19 per cent, which is comparable to that achieved in high-efficiency phosphorescence-based OLEDs.

Highly efficient blue electroluminescence based on thermally activated delayed fluorescence.

Organic compounds that exhibit highly efficient, stable blue emission are required to realize inexpensive organic light-emitting diodes for future displays and lighting applications. Here, we define the design rules for increasing the electroluminescence efficiency of blue-emitting organic molecules that exhibit thermally activated delayed fluorescence. We show that a large delocalization of the highest occupied molecular orbital and lowest unoccupied molecular orbital in these charge-transfer compounds enhances the rate of radiative decay considerably by inducing a large oscillator strength even when there is a small overlap between the two wavefunctions. A compound based on our design principles exhibited a high rate of fluorescence decay and efficient up-conversion of triplet excitons into singlet excited states, leading to both photoluminescence and internal electroluminescence quantum yields of nearly 100%.

Triarylboron-Based Fluorescent Organic Light-Emitting Diodes with External Quantum Efficiencies Exceeding 20 .

Triarylboron compounds have attracted much attention, and found wide use as functional materials because of their electron-accepting properties arising from the vacant p orbitals on the boron atoms. In this study, we design and synthesize new donor-acceptor triarylboron emitters that show thermally activated delayed fluorescence. These emitters display sky-blue to green emission and high photoluminescence quantum yields of 87-100 % in host matrices. Organic light-emitting diodes using these emitting molecules as dopants exhibit high external quantum efficiencies of 14.0-22.8 %, which originate from efficient up-conversion from triplet to singlet states and subsequent efficient radiative decay from singlet to ground states.

Donor-acceptor-structured 1,4-diazatriphenylene derivatives exhibiting thermally activated delayed fluorescence: design and synthesis, photophysical properties and OLED characteristics.

A new series of luminescent 1,4-diazatriphenylene (ATP) derivatives with various peripheral donor units, including phenoxazine, 9,9-dimethylacridane and 3-(diphenylamino)carbazole, is synthesized and characterized as thermally activated delayed fluorescence (TADF) emitters. The influence of the donor substituents on the electronic and photophysical properties of the materials is investigated by theoretical calculations and experimental spectroscopic measurements. These ATP-based molecules with donor-acceptor-donor (D-A-D) structures can reduce the singlet-triplet energy gap (0.04-0.26 eV) upon chemical modification of the ATP core, and thus exhibit obvious TADF characteristics in solution and doped thin films. As a demonstration of the potential of these materials, organic light-emitting diodes containing the D-A-D-structured ATP derivatives as emitters are fabricated and tested. External electroluminescence quantum efficiencies above 12% and 8% for green- and sky-blue-emitting devices, respectively, are achieved.

Quantitative prediction of rate constants and its application to organic emitters.

Many phenomena in nature consist of multiple elementary processes. If we can predict all the rate constants of respective processes quantitatively, we can comprehensively predict and understand various phenomena. Here, we report that it is possible to quantitatively predict all related rate constants and quantum yields without conducting experiments, using multiple-resonance thermally activated delayed fluorescence (MR-TADF) as an example. MR-TADFs are excellent emitters because of its narrow emission, high luminescence efficiency, and chemical stability, but they have one drawback: slow reverse intersystem crossing (RISC), leading to efficiency roll-off and reduced device lifetime. Here, we show a quantum chemical calculation method for quantitatively obtaining all the rate constants and quantum yields. This study reveals a strategy to improve RISC without compromising other important factors: radiative decay rate constants, photoluminescence quantum yields, and emission linewidths. Our method can be applied in a wide range of research fields, providing comprehensive understanding of the mechanism including the time evolution of excitons.

Leuco Ethyl Violet as Self-Activating Prodrug Photocatalyst for In Vivo Amyloid-Selective Oxygenation.

Aberrant aggregates of amyloid-ß (Aß) and tau protein (tau), called amyloid, are related to the etiology of Alzheimer disease (AD). Reducing amyloid levels in AD patients is a potentially effective approach to the treatment of AD. The selective degradation of amyloids via small molecule-catalyzed photooxygenation in vivo is a leading approach; however, moderate catalyst activity and the side effects of scalp injury are problematic in prior studies using AD model mice. Here, leuco ethyl violet (LEV) is identified as a highly active, amyloid-selective, and blood-brain barrier (BBB)-permeable photooxygenation catalyst that circumvents all of these problems. LEV is a redox-sensitive, self-activating prodrug catalyst; self-oxidation of LEV through a hydrogen atom transfer process under photoirradiation produces catalytically active ethyl violet (EV) in the presence of amyloid. LEV effectively oxygenates human Aß and tau, suggesting the feasibility for applications in humans. Furthermore, a concept of using a hydrogen atom as a caging group of a reactive catalyst functional in vivo is postulated. The minimal size of the hydrogen caging group is especially useful for catalyst delivery to the brain through BBB.

Organic luminescent molecule with energetically equivalent singlet and triplet excited states for organic light-emitting diodes.

We demonstrate an organic molecule with an energy gap between its singlet and triplet excited states of almost zero (ΔE(ST) ∼ 0 eV). Such separation was realized through proper combination of an electron-donating indolocarbazole group and a diphenyltriazine electron-accepting moiety. Calculated and measured ΔE(ST) were 0.003 and 0.02 eV, respectively. A total photoluminescence efficiency of 59% ± 2% with 45% ± 2% from a delayed component and 14% ± 2% from a prompt component was obtained for a doped film. Organic light emitting diodes containing this molecule as an emitting dopant exhibited an unexpectedly high external electroluminescence efficiency of η(EQE) = 14% ± 1%.

Solvent effect on thermally activated delayed fluorescence by 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene.

Thermally activated delayed fluorescence (TADF) is fluorescence arising from a reverse intersystem crossing (RISC) from the lowest triplet (T1) to the singlet excited state (S1), where these states are separated by a small energy gap (ΔEst), followed by a radiative transition to the ground state (S0). Rate constants relating TADF processes in 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) were determined at four different solvent polarities (toluene, dichloromethane, ethanol, and acetonitrile). We revealed that the rate constant of RISC, kRISC, which is the most important factor for TADF, was significantly enhanced by a reduced ΔEst in more polar solvents. The smaller ΔEst was mainly attributable to a stabilization of the S1 state. This stabilization also induced a Stokes shift in fluorescence through a relatively large change of the dipole moment between S1 and S0 states (17 D). Despite of this factor, we observed a negative correlation between ΔEst and efficiency of the delayed fluorescence (φd). This was ascribed to a lower intersystem crossing rate, kISC, and increased nonradiative decay from S1, k(s)nrs, in polar solvents.

Design of efficient thermally activated delayed fluorescence materials for pure blue organic light emitting diodes.

Efficient thermally activated delayed fluorescence (TADF) has been characterized for a carbazole/sulfone derivative in both solutions and doped films. A pure blue organic light emitting diode (OLED) based on this compound demonstrates a very high external quantum efficiency (EQE) of nearly 10% at low current density. Because TADF only occurs in a bipolar system where donor and acceptor centered (3)ππ* states are close to or higher than the triplet intramolecular charge transfer ((3)CT) state, control of the π-conjugation length of both donor and acceptor is considered to be as important as breaking the π-conjugation between them in blue TADF material design.

Comprehensive understanding of multiple resonance thermally activated delayed fluorescence through quantum chemistry calculations.

Molecules that exhibit multiple resonance (MR) type thermally activated delayed fluorescence (TADF) are highly efficient electroluminescent materials with narrow emission spectra. Despite their importance in various applications, the emission mechanism is still controversial. Here, a comprehensive understanding of the mechanism for a representative MR-TADF molecule (5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene, DABNA-1) is presented. Using the equation-of-motion coupled-cluster singles and doubles method and Fermi's golden rule, we quantitatively reproduced all rate constants relevant to the emission mechanism; prompt and delayed fluorescence, internal conversion (IC), intersystem crossing, and reverse intersystem crossing (RISC). In addition, the photoluminescence quantum yield and its prompt and delayed contributions were quantified by calculating the population kinetics of excited states and the transient photoluminescence decay curve. The calculations also revealed that TADF occurred via a stepwise process of 1) thermally activated IC from the electronically excited lowest triplet state T1 to the second-lowest triplet state T2, 2) RISC from T2 to the lowest excited singlet state S1, and 3) fluorescence from S1.

Imidazole Acceptor for Both Vacuum-Processable and Solution-Processable Efficient Blue Thermally Activated Delayed Fluorescence.

The members of the imidazole family have been widely used for electron transporting, host, conventional fluorescent, and phosphorescent materials. Although the imidazole core also has great potential as an acceptor segment of deep-blue thermally activated delayed fluorescence (TADF) owing to its high triplet energy, the emission color of imidazole-based TADF organic light-emitting diodes (OLEDs) has so far been limited to blue to green. In this work, four acridan-imidazole systems are theoretically designed aiming for deep- or pure-blue emitters. All four emitters exhibit deep-blue to blue emission owing to the high energy levels of the lowest excited singlet states, exhibiting y coordinates of Commission Internationale de l'Eclairage coordinates between 0.06 and 0.26. The molecule composed of a trifluoromethyl-substituted benzimidazole acceptor in combination with a tetramethyl-9,10-dihydroacridine donor (named MAc-FBI) achieves a high maximum external quantum efficiency (EQEMAX) of 13.7% in its application to vacuum-processed OLEDs. The emitter has high solubility even in ecofriendly nonhalogenated solvents, which motivates us to fabricate solution-processed MAc-FBI-based OLEDs, resulting in an even higher EQEMAX of 16.1%.

Correlated Triplet Pair Formation Activated by Geometry Relaxation in Directly Linked Tetracene Dimer (5,5'-Bitetracene).

Singlet fission (SF) materials have the potential to overcome the traditional external quantum efficiency limits of organic light-emitting diodes (OLEDs). In this study, we theoretically designed an intramolecular SF molecule, 5,5'-bitetracene (55BT), in which two tetracene units were directly connected through a C-C bond. Using quantum chemical calculation and the Fermi golden rule, we show that 55BT undergoes efficient SF induced by geometry relaxation in a locally excited singlet state, 1(S0S1). Compared with another high-performing SF system, the tetracene dimer in the crystalline state, 55BT has advantages when used in doped systems owing to covalent bonding of the two tetracene units. This feature makes 55BT a promising candidate triplet sensitizer for near-infrared OLEDs.

Conformation Control of Iminodibenzyl-Based Thermally Activated Delayed Fluorescence Material by Tilted Face-to-Face Alignment With Optimal Distance (tFFO) Design.

In organic light-emitting diodes (OLEDs), all triplet excitons can be harvested as light via reverse intersystem crossing (RISC) based on thermally activated delayed fluorescence (TADF) emitters. To realize efficient TADF, RISC should be fast. Thus, to accomplish rapid RISC, in the present study, a novel TADF emitter, namely, TpIBT-tFFO, was reported. TpIBT-tFFO was compared with IB-TRZ, which contains the same electron donor and acceptor segments, specifically iminodibenzyl and triazine moieties. TpIBT-tFFO is based on a recently proposed molecular design strategy called tilted face-to-face alignment with optimal distance (tFFO), whereas IB-TRZ is a conventional through-bond type molecule. According to quantum chemical calculations, a very large RISC rate constant, k RISC, was expected for TpIBT-tFFO because not only the lowest triplet state but also the second lowest triplet state were close to the lowest excited singlet state, as designed in the tFFO strategy. IB-TRZ has two different conformers, leading to dual emission. Conversely, owing to excellent packing, the conformation was fixed to one in the tFFO system, resulting in single-peaked emission for TpIBT-tFFO. TpIBT-tFFO displayed TADF type behavior and afforded higher photoluminescence quantum yield (PLQY) compared to IB-TRZ. The k RISC of TpIBT-tFFO was determined at 6.9 × 106 s-1, which is one of the highest values among molecules composed of only H, C, and N atoms. The external quantum efficiency of the TpIBT-tFFO-based OLED was much higher than that of the IB-TRZ-based one. The present study confirms the effectiveness of the tFFO design to realize rapid RISC. The tFFO-based emitters were found to exhibit an additional feature, enabling the control of the molecular conformations of the donor and/or acceptor segments.

Blue organic light-emitting diodes realizing external quantum efficiency over 25% using thermally activated delayed fluorescence emitters.

Improving the performance of blue organic light-emitting diodes (OLEDs) is needed for full-colour flat-panel displays and solid-state lighting sources. The use of thermally activated delayed fluorescence (TADF) is a promising approach to efficient blue electroluminescence. However, the difficulty of developing efficient blue TADF emitters lies in finding a molecular structure that simultaneously incorporates (i) a small energy difference between the lowest excited singlet state (S1) and the lowest triplet state (T1), ΔE ST, (ii) a large oscillator strength, f, between S1 and the ground state (S0), and (iii) S1 energy sufficiently high for blue emission. In this study, we develop TADF emitters named CCX-I and CCX-II satisfying the above requirements. They show blue photoluminescence and high triplet-to-singlet up-conversion yield. In addition, their transition dipole moments are horizontally oriented, resulting in further increase of their electroluminescence efficiency. Using CCX-II as an emitting dopant, we achieve a blue OLED showing a high external quantum efficiency of 25.9%, which is one of the highest EQEs in blue OLEDs reported previously.