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.

Unusual flexibility of transparent poly(methylsilsesquioxane) aerogels by surfactant-induced mesoscopic fiber-like assembly.

High-performance thermal insulators represented by aerogels are regarded as one of the most promising materials for energy savings. However, significantly low mechanical strength has been a barrier for aerogels to be utilized in various social domains such as houses, buildings, and industrial plants. Here, we report a synthetic strategy to realize highly transparent aerogels with unusually high bending flexibility based on poly(methylsilsesquioxane) (PMSQ) network. We have constructed mesoscopic fine fiber-like structures of various sizes in PMSQ gels by the combination of phase separation suppression by tetramethylammonium hydroxide (TMAOH) and mesoscopic fiber-like assembly by nonionic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-b-PPO-b-PEO) type surfactant. The optimized mesoscale structures of PMSQ gels have realized highly transparent and resilient monolithic aerogels with much high bendability compared to those reported in previous works. This work will provide a way to highly insulating materials with glasslike transparency and high mechanical flexibility.

Torsion Angle Analysis of a Thermally Activated Delayed Fluorescence Emitter in an Amorphous State Using Dynamic Nuclear Polarization Enhanced Solid-State NMR.

The torsion angle between donor and acceptor segments of a thermally activated delayed fluorescence (TADF) molecule is one of the most critical factors in determining the performance of TADF-based organic light-emitting diodes (OLEDs) because the torsion angle affects not only the energy gap between the singlet and triplet but also the oscillator strength and spin-orbit coupling. However, the torsion angle is difficult to analyze, because organic molecules are in an amorphous state in OLEDs. Here, we determined the torsion angle of a highly efficient TADF emitter, DACT-II, in an amorphous state by dynamic nuclear polarization enhanced solid-state NMR measurements. From the experimentally obtained chemical shift principal values of 15N on carbazole, we determined the average torsion angle to be 52°. Such quantification of the torsion angles in TADF molecules in amorphous solids will provide deep insight into the TADF mechanism in amorphous OLEDs.

Operando ESR observation in thermally activated delayed fluorescent organic light-emitting diodes.

Organic light-emitting diodes (OLEDs) using thermally activated delayed fluorescence (TADF) materials have advantages over OLEDs using conventional fluorescent materials or high-cost phosphorescent materials, including higher efficiency and lower cost. To attain further high device performance, clarifying internal charge states in OLEDs at a microscopic viewpoint is crucial; however, only a few such studies have been performed. Here, we report a microscopic investigation into internal charge states in OLEDs with a TADF material by electron spin resonance (ESR) at a molecular level. We observed operando ESR signals of the OLEDs and identified their origins due to a hole-transport material PEDOT:PSS, gap states at an electron-injection layer, and a host material CBP in the light-emitting layer by performing density functional theory calculation and studying thin films used in the OLEDs. The ESR intensity varied with increasing applied bias before and after the light emission. We find leakage electrons in the OLED at a molecular level, which is suppressed by a further electron-blocking layer MoO3 between the PEDOT:PSS and light-emitting layer, resulting in the enhancement of luminance with a low-voltage drive. Such microscopic information and applying our method to other OLEDs will further improve the OLED performance from the microscopic viewpoint.

Conformational, Host, and Vibrational Effects Giving Rise to Dynamic TADF Behavior in the Through-Space Charge Transfer, Triptycene Bridged Acridine-Triazine Donor Acceptor TADF Molecule TpAT-tFFO.

We present a joint experimental and theoretical study of the through-space charge transfer (CT) TADF molecule TpAT-tFFO. The measured fluorescence has a singular Gaussian line shape but two decay components, coming from two distinct molecular CT conformers, energetically only 20 meV apart. We determined the intersystem crossing rate (1 × 107 s-1) to be 1 order of magnitude faster than radiative decay, and prompt emission (PF) is therefore quenched within 30 ns, leaving delayed fluorescence (DF) observable from 30 ns onward as the measured reverse intersystem crossing (rISC) rate is >1 × 106 s-1, yielding a DF/PF ratio >98%. Time-resolved emission spectra measured between 30 ns and 900 ms in films show no change in the spectral band shape, but between 50 and 400 ms, we observe a ca. 65 meV red shift of the emission, ascribed to the DF to phosphorescence transition, with the phosphorescence (lifetime >1 s) emanating from the lowest 3CT state. A host-independent thermal activation energy of 16 meV is found, indicating that small-amplitude vibrational motions (∼140 cm-1) of the donor with respect to the acceptor dominate rISC. TpAT-tFFO photophysics is dynamic, and these vibrational motions drive the molecule between maximal rISC rate and high radiative decay configurations so that the molecule can be thought to be "self-optimizing" for the best TADF performance.

Multiple donor-acceptor design for highly luminescent and stable thermally activated delayed fluorescence emitters.

A considerable variety of donor-acceptor (D-A) combinations offers the potential for realizing highly efficient thermally activated delayed fluorescence (TADF) materials. Multiple D-A type compounds are one of the promising families of TADF materials in terms of stability as well as efficiencies. However, those emitters are always composed of carbazole-based donors despite a wide choice of moieties used in linearly linked single D-A molecules. Herein, we developed a multiple D-A type TADF compound with two distinct donor units of 9,10-dihydro-9,9-dimethylacridine (DMAC) and carbazole as the hetero-donor design. The new emitter exhibits high photoluminescence quantum yield (PLQY) in various conditions including polar media blend and high concentrations. Organic light-emitting diodes (OLEDs) showed a reasonably high external quantum efficiency (EQE). In addition, we revealed that the multiple-D-A type molecules showed better photostability than the single D-A type molecules, while the operational stability in OLEDs involves dominant other factors.

A Donor-Acceptor 10-Cycloparaphenylene and Its Use as an Emitter in an Organic Light-Emitting Diode.

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 λPL = 475 nm, ΦPL = 29%, and triexponential emission decays with τPL of 4.4, 46.3, and 907.8 ns. Solution-processed OLEDs using 4PXZPh-[10]CPP exhibited sky-blue emission with an λEL of 465 nm and an EQEmax of 1.0%.

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.

Robust Spirobifluorene Core Based Hole Transporters with High Mobility for Long-Life Green Phosphorescent Organic Light-Emitting Devices.

Using a tailored high triplet energy hole transport layer (HTL) is a suitable way to improve the efficiency and extend the lifetime of organic light-emitting devices (OLEDs), which can use all molecular excitons of singlets and triplets. In this study, dibenzofuran (DBF)-end-capped and spirobifluorene (SBF) core-based HTLs referred as TDBFSBF1 and TDBFSBF2 were effectively developed. TDBFSBF1 exhibited a high glass transition temperature of 178 °C and triplet energy of 2.5 eV. Moreover, a high external quantum efficiency of 22.0 %, long operational lifetime at 50 % of the initial luminance of 89,000 h, and low driving voltage at 1000 cd m-2 of 2.95 V were achieved in green phosphorescent OLEDs using TDBFSBF1. Further, a high-hole mobility µh value of 1.9×10-3  cm2 V-1 s-1 was recorded in TDBFSBF2. A multiscale simulation successfully reproduced the experimental µh values and indicated that the reorganization energy was the primary factor in determining the mobility differences among these SBF core based HTLs.

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%.

Highly Efficient and Stable Blue Organic Light-Emitting Diodes based on Thermally Activated Delayed Fluorophor with Donor-Void-Acceptor Motif.

Thermally activated delayed fluorophores (TADF) with donor-acceptor (D-A) structures always face strong conjugation between donor and acceptor segments, rendering delocalized new molecular orbitals that go against blue emission. Developing TADF emitters with blue colors, high efficiencies, and long lifetimes simultaneously is therefore challenging. Here, a D-void-A structure with D and A moieties connected at the void-position where the frontier orbital from donor and acceptor cannot be distributed, resulting in nonoverlap of the orbitals is proposed. A proof-of-the-concept TADF emitter with 3,6-diphenyl-9H-carbazole (D) connected at the 3'3-positions of 9H-xanthen-9-one (A), the void carbon-atom with no distribution of the highest occupied molecular orbital (HOMO) of A-segment, realizes more efficient and blue-shifted emission compared with the contrast D-A isomers. The deeper HOMO-2 of A is found to participate into conjugation rather than HOMO, providing a wider-energy-gap. The corresponding blue device exhibits a y color coordinate (CIEy ) of 0.252 and a maximum external quantum efficiency of 27.5%. The stability of this compound is further evaluated as a sensitizer for a multiple resonance fluorophore, realizing a long lifetime of ≈650 h at an initial luminance of 100 cd m-2 with a CIEy of 0.195 and a narrowband emission with a full-width-at-half-maxima of 21 nm.

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.

Effect of a twin-emitter design strategy on a previously reported thermally activated delayed fluorescence organic light-emitting diode.

In this work we showcase the emitter DICzTRZ in which we employed a twin-emitter design of our previously reported material, ICzTRZ. This new system presented a red-shifted emission at 488 nm compared to that of ICzTRZ at 475 nm and showed a comparable photoluminescence quantum yield of 57.1% in a 20 wt % CzSi film versus 63.3% for ICzTRZ. The emitter was then incorporated within a solution-processed organic light-emitting diode that showed a maximum external quantum efficiency of 8.4%, with Commission Internationale de l'Éclairage coordinate of (0.22, 0.47), at 1 mA cm-2.

Near-Unity Singlet Fission on a Quantum Dot Initiated by Resonant Energy Transfer.

The conversion of a high-energy photon into two excitons using singlet fission (SF) has stimulated a variety of studies in fields from fundamental physics to device applications. However, efficient SF has only been achieved in limited systems, such as solid crystals and covalent dimers. Here, we established a novel system by assembling 4-(6,13-bis(2-(triisopropylsilyl)ethynyl)pentacen-2-yl)benzoic acid (Pc) chromophores on nanosized CdTe quantum dots (QDs). A near-unity SF (198 ± 5.7%) initiated by interfacial resonant energy transfer from CdTe to surface Pc was obtained. The unique arrangement of Pc determined by the surface atomic configuration of QDs is the key factor realizing unity SF. The triplet-triplet annihilation was remarkably suppressed due to the rapid dissociation of triplet pairs, leading to long-lived free triplets. In addition, the low light-harvesting ability of Pc in the visible region was promoted by the efficient energy transfer (99 ± 5.8%) from the QDs to Pc. The synergistically enhanced light-harvesting ability, high triplet yield, and long-lived triplet lifetime of the SF system on nanointerfaces could pave the way for an unmatched advantage of SF.

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.

Exact Solution of Kinetic Analysis for Thermally Activated Delayed Fluorescence Materials.

The photophysical analysis of thermally activated delayed fluorescence (TADF) materials has become instrumental for providing insights into their stability and performance, which is not only relevant for organic light-emitting diodes but also for other applications such as sensing, imaging, and photocatalysis. Thus, a deeper understanding of the photophysics underpinning the TADF mechanism is required to push materials design further. Previously reported analyses in the literature of the kinetics of the various processes occurring in a TADF material rely on several a priori assumptions to estimate the rate constants for forward and reverse intersystem crossing. In this report, we demonstrate a method to determine these rate constants using a three-state model together with a steady-state approximation and, importantly, no additional assumptions. Further, we derive the exact rate equations, greatly facilitating a comparison of the TADF properties of structurally diverse emitters and providing a comprehensive understanding of the photophysics of these systems.

Multichromophore Molecular Design for Thermally Activated Delayed-Fluorescence Emitters with Near-Unity Photoluminescence Quantum Yields.

Three multichromophore thermally activated delayed fluorescence (TADF) molecules, p-di2CzPN, m-di2CzPN, and 1,3,5-tri2CzPN, were synthesized and characterized. These molecules were designed by connecting the TADF moiety 4,5-di(9H-carbazol-9-yl)phthalonitrile (2CzPN) to different positions of a central benzene ring scaffold. Three highly soluble emitters all exhibited near-quantitative photoluminescence quantum yields (ΦPL) in toluene. High ΦPLs were also achieved in doped films, 59 and 70% for p-di2CzPN and m-di2CzPN in 10 wt % DPEPO doped film, respectively, and 54% for 1,3,5-tri2CzPN in 20 wt % doped CBP films. The rate constant of reverse intersystem crossing (kRISC) for p-di2CzPN and m-di2CzPN in DPEPO films reached 1.1 × 105 and 0.7 × 105 s-1, respectively, and kRISC for 1,3,5-tri2CzPN in the CBP film reached 1.7 × 105 s-1. A solution-processed organic light-emitting diode based on 1,3,5-tri2CzPN exhibited a sky-blue emission with CIE coordinates of (0.22, 0.44) and achieved a maximum external quantum efficiency of 7.1%.

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.

Efficient Direct Reverse Intersystem Crossing between Charge Transfer-Type Singlet and Triplet States in a Purely Organic Molecule.

The front cover artwork is provided by the group of Prof. Hironori Kaji, Dr. Yoshimasa Wada, and Mr. Yasuaki Wakisaka (Institute for Chemical Research, Kyoto University). The image shows our designed emitter molecule, MA-TA, possessing charge-transfer (CT) character in both triplet and singlet states. The dynamic flexibility of molecules allows effective reverse intersystem crossing (RISC) and MA-TA show excellent performances in any kinds of hosts. Read the full text of the Article at 10.1002/cphc.202001013.