A surprising
yet highly practical approach to improve the performance
of a TADF exciplex blend is reported. Using the TSBPA donor and PO-T2T
acceptor to form an exciplex, we are able to blue shift the emission,
increase PLQY from 58 to 80%, and increase the device EQE from 14.8
to 19.2% by simply diluting the exciplex with an inert high triplet
energy host materialhere either UGH-3 or DPEPO. These effects
are explained in terms of an increasing donor–acceptor distance
and associated charge separation, while different behaviors observed
in the different hosts are attributed to different energy barriers
to electron transfer through the host. We expect that the observed
performance-enhancing effects of dilution will be general to different
exciplex blends and host materials and offer a new way to optimize
the electrical properties of exciplex emission layers with narrow
blue emission.
New thermally activated delayed fluorescence (TADF) blue emitter molecules based on the known donor−acceptor−donor (D−A−D)type TADF molecule, 2,7-bis(9,9-dimethylacridin-10-yl)-9,9-dimethylthioxanthene-S,S-dioxide (DDMA-TXO2), are reported. The motivation for the present investigation is via the use of rational molecular design, based on DDMA-TXO2, to elevate the organic light emitting diode (OLED) performance and obtain deeper blue color coordinates. To achieve this goal, the strength of the donor (D) unit and acceptor (A) units have been tuned with methyl substituents. The methyl functionality on the acceptor was also expected to modulate the D−A torsion angle in order to obtain a blue shift in the electroluminescence. The effect of regioisomeric structures has also been investigated. Herein, we report the photophysical, electrochemical, and single-crystal X-ray crystallography data to assist with the successful OLED design. The methyl substituents on the DDMA-TXO2 framework have profound effects on the photophysics and color coordinates of the emitters. The weak electron-donating methyl groups alter the redox properties of the D and A units and consequently affect the singlet and triplet levels but not the energy gap (ΔE ST ). By systematically manipulating all of the aforementioned factors, devices have been obtained with acceptor-substituted III with a maximum external quantum efficiency of 22.6% and Commission Internationale de l'E ́clairage coordinates of (0.15, 0.18) at 1000 cd m −2 .
The not so elusive carbenoid fluoroiodomethyllithium disclosed its electrophilic nature in an unprecedented direct and stereoselective fluorocyclopropanation of allylic alcohols.
The first direct and straightforward nucleophilic fluoromethylation of organic compounds is reported. The tactic employs a "fleeting" lithium fluorocarbenoid (LiCHF) generated from commercially available fluoroiodomethane. Precise reaction conditions were developed for the generation and synthetic exploitation of such a labile species. The versatility of the strategy is showcased in ca. 50 examples involving a plethora of electrophiles. Highly valuable chemicals such as fluoroalcohols, fluoroamines, and fluoromethylated oxygenated heterocycles could be prepared in very good yields through a single synthetic operation. The scalability of the reaction and its application to complex molecular architectures (e.g., steroids) are documented.
An
expeditious, high-yielding synthesis of rare α-fluoroepoxides
and α-fluoroaziridines through the addition of the unkown fluoroiodomethyllithium
(LiCHIF)formed via deprotonation the commercially available
fluoroiodomethane with
a lithium amide baseto carbonyl-like compounds is documented.
The ring-closure reactions,
leading to α-fluorinated three-membered heterocycles, rely on
the diversely reactive C–I and C–F bonds. Excellent
chemoselectivity was observed in the presence of
highly sensitive functionalitiesaldehyde, ketone, nitrile,
alkenewhich
remained untouched during the homologation sequence.
Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry, and provide attractive bioisosteres for sulfonamides. However, there remain few operationally simple methods for their preparation. Here, the synthesis of NH‐sulfonimidamides is achieved directly from sulfenamides, themselves readily formed in one step from amines and disulfides. A highly chemoselective and one‐pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source, and in the presence of 1 equivalent of acetic acid. A wide range of functional groups are tolerated under the developed reaction conditions, which also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel S≡N sulfanenitrile species as intermediates. Several alkoxy‐amino‐λ6‐sulfanenitriles are prepared with different alcohols, and shown to be alkylating agents to a range of nucleophiles.
In the field of organic synthesis, the advent of flow chemistry and flow microreactor technology represented a tremendous novelty in the way of thinking and performing chemical reactions, opening the doors to poorly explored or even impossible transformations using batch methods. In this Concept article, we would like to highlight the impact of flow chemistry for exploiting highly reactive organometallic reagents, and how, alongside the well‐known advantages concerning safety, scalability, and productivity, flow chemistry makes possible processes that are impossible to control by using the traditional batch approach.
The photophysics of an exciplex state formed between a small molecule and a polymer is investigated in this work. The results obtained with this blend show the strong potential of polymer−small-molecule blends for triplet harvesting in organic light-emitting diodes (OLEDs) via thermally activated delayed fluorescence. The exciplex formed between poly(N-vinylcarbazole) (PVK) and 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T) shows yellow-green emission and is applied in solution-processed OLEDs. The excellent film-forming properties in this blend allow easy spin coating and potential use in other solutionprocessing techniques, such as slot die coating. In this work, we critically address the reverse intersystem crossing mechanism in the presented exciplex system, including the role of local triplet states. Moreover, we bring a clear physical meaning to the decay components of the exciplex emission, including the decay occurring in a power-law fashion that is often ignored in the literature.
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