Recent advances in highly-efficient near infrared OLED emitters

Near infrared (NIR) light (700–1400 nm) can be used in numerous biological/medical as well as technological applications. In this work we review the most recent examples of highly efficient NIR organic light-emitting diode (OLED) emitters among the most relevant types of luminophores: platinum(II), iridium(III), and osmium(II) complexes, unimolecular thermally activated delayed fluorescence (TADF) emitters and exciplexes, fluorescent dyes, and the emerging group of stable luminescent radicals. We dive into the structural design principles of emitters with improved NIR efficiency. In our discussion we consider unimolecular emission as well as that arising from aggregated luminophores, as the latter often leads to a longer wavelength NIR. Our analysis of numerous emitters from various groups concludes, without a doubt, that platinum(II) complexes present superior efficiency in nearly all wavelengths from 700 to 1000 nm. We report on an apparent NIR boundary line, which appears to be a current limitation for NIR OLED efficiency. Presently, virtually only platinum(II) complexes exceed the efficiency limit set out by this boundary. So far efficient OLEDs, i.e. >1% external quantum efficiency, emitting significantly beyond 1000 nm have not yet been reported

Detection of acetone vapours using solution-processed tin oxide thin-film transistors

Abnormal concentrations of volatile organic compounds (VOCs) in human breathe can be used as disease-specific biomarkers for the non-invasive diagnosis of medical conditions, such as acetone for diabetes. Solution-processed bottom gate top contact metal oxide thin-film transistors (TFTs) are used to detect acetone vapours, as part of a proof-of-concept study. The effect of increasing annealing temperature (T) and channel length (L) on electrical and sensing performance are explored. Drain current (Ids) increases following exposure as acetone undergoes a redox reaction with the adsorbed oxygen species on the semiconductor surface, which results in free electrons being released back into the conduction band. Responsivity (R) is maximized at negative bias (Vgs < 0). For L = 50 μm, the peak R of the TFT annealed at 450 °C is three times greater than that of the TFT annealed at 350 °C, with Vgs = − 37.5 V and − 33 V, respectively

Optical and Polarity Control of Donor–Acceptor Conformation and Their Charge-Transfer States in Thermally Activated Delayed-Fluorescence Molecules

This study reports two novel D–A–D molecules, 2,7-bis(phenothiazin-10-yl)-9,9-dimethylthioxanthene-S,S-dioxide (DPT-TXO2) and 2,7-bis(1-methylphenothiazin-10-yl)-9,9-dimethylthioxanthene-S,S-dioxide (DMePT-TXO2), where the latter differs by only a methyl group incorporated on each of the donor units. DMePT-TXO2 in solution and in solid state shows dual charge-transfer (CT) emission. The CT states come from two distinctive conformations between the D and A units. Experiments show that the emission contribution of each state can be controlled by the polarity of the environment and by the excitation energy. Also, how the different conformers can be used to control the TADF mechanism is analyzed in detail. These results are important as they give a more in-depth understanding about the relation between molecular conformation and the TADF mechanism, thereby facilitating the design of new TADF molecules

Fine‐Tuning the Photophysics of Donor‐Acceptor (D‐A 3 ) Thermally Activated Delayed Fluorescence Emitters Using Isomerisation

Here two D–A3 regioisomers, comprising three dibenzothiophene-S,S-dioxide acceptor units attached to a central triazatruxene core, are studied. Both molecules show thermally activated delayed fluorescence (TADF), however, the efficiency of the TADF mechanism is strongly affected by the D–A substitution position. The meta- substituted emitter (1 b) shows a slightly higher-lying singlet charge transfer state and a lower-lying triplet state than that observed in the para- substituted emitter (1 a), resulting in a larger singlet–triplet splitting (ΔEST) of 0.28 eV compared to only 0.01 eV found in 1 a. As expected, this ΔEST difference strongly impacts the reverse intersystem crossing (rISC) rates and the para- isomer 1 a exhibits a much faster delayed fluorescence emission. Calculations show that the triplet energy difference between the two isomers is due to steric hindrance variances along the donor–acceptor rotation axis in these molecules: as 1 b is less restricted, rotation of its acceptor unit leads to a lower T1 energy, further away from the region of high density of states (the region where larger vibronic coupling is found, favouring rISC). Therefore, our results show how the substitution pattern has a marked effect on triplet state energies and character, verifying the key structural designs for highly efficient TADF materials

Exact solution of kinetic analysis for thermally activated delayed fluorescence materials

Research at Kyushu, Kyoto and St Andrews Universities was supported by EPSRC and JSPS Core to Core grants (JSPS Core-to-core Program; EPSRC grant number EP/R035164/1). Authors are also grateful for financial support from the Program for Building Regional Innovation Ecosystems of the Ministry of Education, Culture, Sports, Science and Technology, Japan, JST ERATO Grant JPMJER1305, JSPS KAKENHI JP20H05840, and Kyulux Inc.The photophysical analysis of thermally activated delayed fluorescence (TADF) materials has become instrumental to providing insight into their stability and performance, which is not only relevant for organic light-emitting diodes (OLED), 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 (ISC and RISC, respectively). 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.PostprintPostprintPeer reviewe

Delayed Fluorescence by Triplet–Triplet Annihilation from Columnar Liquid Crystal Films

Delayed fluorescence (DF) by triplet–triplet annihilation (TTA) is observed in solutions of a benzoperylene-imidoester mesogen that shows a hexagonal columnar mesophase at room temperature in the neat state. A similar benzoperylene-imide with a slightly smaller HOMO–LUMO gap, that also is hexagonal columnar liquid crystalline at room temperature, does not show DF in solution, and mixtures of the two mesogens show no DF in solution either, because of collisional quenching of the excited triplet states on the imidoester by the imide. In contrast, DF by TTA from the imide but not from the imidoester is observed in condensed films of such mixtures, even though neat films of either single material are not displaying DF. In contrast to the DF from the monomeric imidoester in solution, DF of the imide occurs from dimeric aggregates in the blend films, assisted by the imidoester. Thus, the close contact of intimately stacked molecules of the two different species in the columnar mesophase leads to a unique mesophase-assisted aggregate DF. This constitutes the first observation of DF by TTA from the columnar liquid crystalline state. If the imide is dispersed in films of polybromostyrene, which provides an external heavy-atom effect facilitating triplet formation, DF is also observed. Organic light-emitting diodes (OLEDs) devices incorporating these liquid crystal molecules demonstrated high external quantum efficiency (EQE). On the basis of the literature and to the best of our knowledge, the EQE reported is the highest among nondoped solution-processed OLED devices using a columnar liquid crystal molecule as the emitting layer

The Genus Caesalpinia L. (Caesalpiniaceae): Phytochemical and Pharmacological Characteristics

The genus Caesalpinia (Caesalpiniaceae) has more than 500 species, many of which have not yet been investigated for potential pharmacological activity. Several classes of chemical compounds, such as flavonoids, diterpenes, and steroids, have been isolated from various species of the genus Caesalpinia. It has been reported in the literature that these species exhibit a wide range of pharmacological properties, including antiulcer, anticancer, antidiabetic, anti-inflammatory, antimicrobial, and antirheumatic activities that have proven to be efficacious in ethnomedicinal practices. in this review we present chemical and pharmacological data from recent phytochemical studies on various plants of the genus Caesalpinia.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG)Univ Fed Alfenas, Inst Chem, BR-37130000 Alfenas, MG, BrazilUniversidade Federal de São Paulo, Inst Environm Chem & Pharmaceut Sci, BR-09972 Diadema, SP, BrazilUniversidade Federal de São Paulo, Inst Environm Chem & Pharmaceut Sci, BR-09972 Diadema, SP, BrazilWeb of Scienc

An unusual plank-shaped nematogen with a graphene nanoribbon core

A [12]phenacene exclusively decorated with four lateral hexylester substituents self-assembles into a nematic liquid crystal glass on cooling after melting at high temperature. This uniaxial nematic organization of a plank-shaped nanographene is unprecedented and in strong contrast to the common design rules for liquid crystals. Highly birefringent samples emitting polarized fluorescence can be obtained in homogeneously planar or twisted waveguiding configurations that are stable against crystallization at and below room temperature and up to 100 °C

The contributions of molecular vibrations and higher triplet levels to the intersystem crossing mechanism in metal-free organic emitters.

Intense, simultaneous, room temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) is observed in a series of donor-acceptor-donor (D–A–D) molecules. This dual-luminescence is stronger in the “angular” isomers, compared to their “linear” regioisomers, which is consistent with an enhanced intersystem crossing (ISC) in the former. Herein, we demonstrate that the small energy gap between the triplet levels, T1-Tn, below the lowest singlet state, S1, in the “angular” regioisomers, enhances the coupling between S1 and T1 states and favors ISC and reverse ISC (rISC). This is consistent with a spin-vibronic mechanism. In the absence of this “triplet ladder”, due to the larger energy difference between T1 and Tn in the “linear” regioisomers, the ISC and rISC are not efficient. Remarkably the enhancement on the ISC rate in the “angular” regioisomers is accompanied by an increase on the rate of internal conversion (IC). These results highlight the contributions of higher triplet excited states and molecular vibronic coupling to harvest triplet states in organic compounds, and casts the TADF and RTP mechanisms into a common conceptual framework