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The complex photokinetics of donor-acceptor-donor triads with varying flexible spacer lengths (n = 4-10 carbon atoms) are investigated in liquid and solid solution, as well as in crystals, by steady-state and transient fluorescence spectroscopy combined with computational studies. For the short spacer (n = 4) in a liquid solution, dynamic charge-transfer (CT) state formation with subsequent, efficient exciplex emission is observed, effectively competing with quenching through electron transfer (eT) via a radical ion pair. In a solid solution, a fluorescent CT static complex is formed upon freezing for all spacer lengths. This allows the observations of a former seminal report on stimuli-responsive high-contrast fluorescence on/off switching in films of the triads to be reassigned (Adv. Mater. 2012, 24, 5487), now providing a holistic picture on varying spacer length. In fact, external stimuli of the film by modulating the geometry of the CT complex, which results in on/off fluorescence switching (for n > 4) or in a change of the emission color (n = 4). The work thus demonstrates how in-depth analysis of complex photophysics can be put to practical use in materials science., (© 2023 Wiley-VCH GmbH.)

Organic light-emitting diodes (OLEDs) that can simultaneously achieve narrowband emission, high efficiency, and circularly polarized luminescence remain a formidable challenge. In this study, a simple strategy is developed to address this challenge. A chiral exciplex-forming co-host is first designed by employing a chiral donor and an achiral acceptor molecule. The chiral exciplex host enables an achiral green multiple-resonance thermally activated delayed fluorescence emitter to achieve high-performance circularly polarized electroluminescence (CP-EL) with a high external quantum efficiency of 33.2%, large electroluminescence dissymmetry factor of 2.8 × 10 -3 , and a small full-width at half-maximum of 42 nm. This work provides a general approach for realizing CP-EL using easily available achiral emitters and can significantly extend the scope of circularly polarized OLEDs., (© 2022 Wiley-VCH GmbH.)

Organic long-persistent luminescent systems (OLPLs) exhibiting long-lasting emission after photoexcitation consist of organic electron donors and acceptors, that are widely used in organic light-emitting diodes (OLEDs). Although OLPLs and OLEDs include very similar excitonic processes, long-lasting emission has never been observed in OLEDs. This study confirms the presence of long-persistent luminescence (LPL) under electrical excitation., (© 2021 Wiley-VCH GmbH.)

The isotope effect is studied in the magneto-electroluminescence (MEL) and pulsed electrically detected magnetic resonance of organic light-emitting diodes based on thermally activated delayed fluorescence (TADF) from donor-acceptor exciplexes that are either protonated (H) or deuterated (D). It is found that at ambient temperature, the exchange of H to D has no effect on the spin-dependent current and MEL responses in the devices. However, at cryogenic temperatures, where the reverse intersystem crossing (RISC) from triplet to singlet exciplex diminishes, a pronounced isotope effect is observed. These results show that the RISC process is not governed by the hyperfine interaction as thought previously, but proceeds through spin-mixing in the triplet exciplex. The observations are corroborated by electrically detected transient spin nutation experiments that show relatively long dephasing time at ambient temperature, and interpreted in the context of a model that involves exchange and hyperfine interactions in the spin triplet exciplex. These findings deepen the understanding of the RISC process in TADF materials., (© 2020 Wiley-VCH GmbH.)

Exciplex system exhibiting thermally activated delayed fluorescence (TADF) holds a considerable potential to improve organic light-emitting diode (OLED) performances. However, the operational lifetime of current exciplex-based devices, unfortunately, falls far behind the requirement for commercialization. Herein, rationally choosing a TADF-type electron acceptor molecule is reported as a new strategy to enhance OLEDs' operating lifetime. A comprehensive study of the exciplex system containing 9,9',9''-triphenyl-9H,9'H,9''H-3,3':6',3''-tercarbazole (Tris-PCz) and triazine (TRZ) derivatives clarifies the relationship between unwanted carrier recombination on acceptor molecules, TADF property of acceptors, and the device degradation event. By employing a proposed "exciton recycling" strategy, a threefold increased operational lifetime can be achieved while still maintaining high-performance OLED properties. In particular, a stable blue OLED that employs this strategy is successfully demonstrated. This research provides an important step for exciplex-based devices toward the significant improvement of operational stability., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Experimental studies to reveal the cooperative relationship between spin, energy, and polarization through intermolecular charge-transfer dipoles to harvest nonradiative triplets into radiative singlets in exciplex light-emitting diodes are reported. Magneto-photoluminescence studies reveal that the triplet-to-singlet conversion in exciplexes involves an artificially generated spin-orbital coupling (SOC). The photoinduced electron parametric resonance measurements indicate that the intermolecular charge-transfer occurs with forming electric dipoles (D +• →A -• ), providing the ionic polarization to generate SOC in exciplexes. By having different singlet-triplet energy differences (ΔE ST ) in 9,9'-diphenyl-9H,9'H-3,3'-bicarbazole (BCzPh):3',3'″,3'″″-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-3-carbonitrile)) (CN-T2T) (ΔE ST = 30 meV) and BCzPh:bis-4,6-(3,5-di-3-pyridylphenyl)-2-methyl-pyrimidine (B3PYMPM) (ΔE ST = 130 meV) exciplexes, the SOC generated by the intermolecular charge-transfer states shows large and small values (reflected by different internal magnetic parameters: 274 vs 17 mT) with high and low external quantum efficiency maximum, EQE max (21.05% vs 4.89%), respectively. To further explore the cooperative relationship of spin, energy, and polarization parameters, different photoluminescence wavelengths are selected to concurrently change SOC, ΔE ST , and polarization while monitoring delayed fluorescence. When the electron clouds become more deformed at a longer emitting wavelength due to reduced dipole (D +• →A -• ) size, enhanced SOC, increased orbital polarization, and decreased ΔE ST can simultaneously occur to cooperatively operate the triplet-to-singlet conversion., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Recently, the external quantum efficiency and lifetime of organic light-emitting diodes (OLEDs) have been dramatically upgraded due to development of organic materials and device structure. In particular, an intramolecular or intermolecular complex based on thermally activated delayed fluorescent (TADF) materials has greatly contributed to improving OLED device performance. Although high external quantum efficiency has been the main objective of the development of TADF materials as hosts and emitters, recent interest has been directed towards the lifetime of TADF-material-based OLEDs. For the past several years, remarkable advances in the lifetime of phosphorescent and TADF OLEDs have been made using TADF materials as hosts or emitters in the emitting layer. Therefore, since TADF materials are useful as both hosts and emitters for a long lifetime, this work discusses the recent progress made in developing TADF materials for long-lifetime OLEDs., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Almost 100% internal quantum efficiency (IQE) is achieved with a green fluorescent organic light-emitting diode (OLED) exhibiting 30% external quantum efficiency (EQE). The OLED comprises an exciplex-forming co-host system doped with a fluorescent dye that has a strong delayed fluorescence as a result of reverse intersystem crossing (RISC); the exciplex-forming co-hosts stimulate energy transfer and charge balance in the system. The orientation of the transition dipole moment of the fluorescent dye is shown to have an influence on the EQE of the device., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)