An unprecedented roll-off ratio in high-performing red TADF OLED emitters featuring 2,3-indole-annulated naphthalene imide and auxiliary donors.

The capability of organic emitters to harvest triplet excitons via a thermally activated delayed fluorescence (TADF) process has opened a new era in organic optoelectronics. Nevertheless, low brightness, and consequently an insufficient roll-off ratio, constitutes a bottleneck for their practical applications in the domain of organic light-emitting diodes (OLEDs). To address this formidable challenge, we developed a new design of desymmetrized naphthalimide (NMI) featuring an annulated indole with a set of auxiliary donors on its periphery. Their perpendicular arrangement led to minimized HOMO-LUMO overlap, resulting in a low energy gap (ΔE ST = 0.05-0.015 eV) and efficient TADF emission with a photoluminescence quantum yield (PLQY) ranging from 82.8% to 95.3%. Notably, the entire set of dyes (NMI-Ind-TBCBz, NMI-Ind-DMAc, NMI-Ind-PXZ, and NMI-Ind-PTZ) was utilized to fabricate TADF OLED devices, exhibiting yellow to red electroluminescence. Among them, red-emissive NMI-Ind-PTZ, containing phenothiazine as an electron-rich component, revealed predominant performance with a maximum external quantum efficiency (EQE) of 23.6%, accompanied by a persistent luminance of 38 000 cd m-2. This results in a unique roll-off ratio (EQE10 000 = 21.6%), delineating a straightforward path for their commercial use in lighting and display technologies.

Facile Functionalization of Ambipolar, Nitrogen-Doped PAHs toward Highly Efficient TADF OLED Emitters.

Despite promising optoelectronic features of N-doped polycyclic aromatic hydrocarbons (PAHs), their use as functional materials remains underdeveloped due to their limited post-functionalization. Facing this challenge, a novel design of N-doped PAHs with D-A-D electronic structure for thermally activated delayed fluorescence (TADF) emitters was performed. Implementing a set of auxiliary donors at the meta position of the protruding phenyl ring of quinoxaline triggers an increase in the charge-transfer property simultaneously decreasing the delayed fluorescence lifetime. This, in turn, contributes to a narrow (0.04-0.28 eV) singlet-triplet exchange energy split (ΔEST) and promotes a reverse intersystem crossing transition that is pivotal for an efficient TADF process. Boosting the electron-donating ability of our N-PAH scaffold leads to excellent photoluminescence quantum yield that was found in a solid-state matrix up to 96% (for phenoxazine-substituted derivatives, under air) with yellow or orange-red emission, depending on the specific compound. Organic light-emitting diodes (OLEDs) utilizing six, (D-A)-D, N-PAH emitters demonstrate a significant throughput with a maximum external quantum efficiency of 21.9% which is accompanied by remarkable luminance values which were found for all investigated devices in the range of 20,000-30,100 cd/m2 which is the highest reported to date for N-doped PAHs investigated in the OLED domain.

Mechanism of Silylation of Vinyl Arenes by Hydrodisiloxanes Driven by Stoichiometric Amounts of Sodium Triethylborohydride-A Combined DFT and Experimental Study.

The reactions of vinyl arenes with hydrodisiloxanes in the presence of sodium triethylborohydride were studied using experimental and computational methods. The expected hydrosilylation products were not detected because triethylborohydrides did not exhibit the catalytic activity observed in previous studies; instead, the product of formal silylation with dimethylsilane was identified, and triethylborohydride was consumed in stoichiometric amounts. In this article, the mechanism of the reaction is described in detail, with due consideration given to the conformational freedom of important intermediates and the two-dimensional curvature of the potential energy hypersurface cross sections. A simple way to reestablish the catalytic character of the transformation was identified and explained with reference to its mechanism. The reaction presented here is an example of the application of a simple transition-metal-free catalyst in the synthesis of silylation products, with flammable gaseous reagents replaced by a more convenient silane surrogate.

Evaluation of Hydroxyl Radical Reactivity by Thioether Group Proximity in Model Peptide Backbone: Methionine versus S-Methyl-Cysteine.

Hydroxyl radicals (HO•) have long been regarded as a major source of cellular damage. The reaction of HO• with methionine residues (Met) in peptides and proteins is a complex multistep process. Although the reaction mechanism has been intensively studied, some essential parts remain unsolved. In the present study we examined the reaction of HO• generated by ionizing radiation in aqueous solutions under anoxic conditions with two compounds representing the simplest model peptide backbone CH3C(O)NHCHXC(O)NHCH3, where X = CH2CH2SCH3 or CH2SCH3, i.e., the Met derivative in comparison with the cysteine-methylated derivative. We performed the identification and quantification of transient species by pulse radiolysis and final products by LC-MS and high-resolution MS/MS after γ-radiolysis. The results allowed us to draw for each compound a mechanistic scheme. The fate of the initial one-electron oxidation at the sulfur atom depends on its distance from the peptide backbone and involves transient species of five-membered and/or six-membered ring formations with different heteroatoms present in the backbone as well as quite different rates of deprotonation in forming α-(alkylthio)alkyl radicals.

Synthesis of Bifunctional Silsesquioxanes and Spherosilicates with Organogermyl Functionalities.

In this paper we present the synthesis of mixed bifunctional compounds of T8 H8 silsesquioxane and spherosilicate (HSiMe2 O)8 Si8 O12 derivatives via platinum-catalyzed hydrosilylation of alkenylgermanes and olefins. To the best of our knowledge, this is the first literature example of bifunctional compounds with organogermyl functionalities. Eleven mixed systems with a variety of substituents (Si-H, alkyl, germyl, epoxy, and hydroxy) were prepared and fully characterized by NMR spectroscopy. Additionally, our research includes a real-time FT-IR study of the synthesis of these bifunctional compounds of the general formula (R)8-m (GeR'3 (CH2 )n+2 R)m Si8 O12 . and (R''(CH2 )2 R)8-m (GeR'3 (CH2 )2 R)m Si8 O12 where m∼4.

Synthesis and Hydrosilylation of Vinyl-Substituted Open-Cage Silsesquioxanes with Phenylsilanes: Regioselective Synthesis of Trifunctional Silsesquioxanes.

Herein, we report an efficient synthesis and functionalization of trifunctional open-cage-type silsesquioxanes. The method proposed has been successfully applied for the synthesis of a library of incompletely condensed silsesquioxanes with vinyldiorganosilyl functional groups, which allows further modification. Detailed studies of hydrosilylation of sterically different open-cage vinylsilsesquioxanes with a wide spectrum of phenylsilanes catalyzed by platinum and rhodium compounds are also reported. The influence of the reaction parameters, types of reagents, and catalysts employed on the efficiency of the process was examined. Optimization of the process based on the above results permitted the design of a very attractive method for the synthesis of multifunctionalized silsesquioxanes with excellent yields and regioselectivity. Moreover, the results allowed the choice of the most efficient catalyst whose application led to the selective formation of substituted open-cage silsesquioxanes. These new compounds have been fully characterized and studied in terms of their thermal properties.

Dialkenylgermanes as Precursors of Silsesquioxane-based Macromolecular Structures.

Herein we report a study of highly efficient platinum-catalyzed hydrosilylation of dialkenylgermanes with silsesquioxanes and spherosilicates. The use of divinyl- and diallylgermanes allowed the synthesis of new classes of compounds, i. e., dumbbell-type systems, silsesquioxanes with alkenyl pendant group, and oligomeric derivatives. The results are supported by detailed data from in situ FT-IR and NMR measurements, enabling precise monitoring of the reaction progress and determination of regioselectivity of the formed products.

Introduction of organogermyl functionalities to cage silsesquioxanes.

In this work, we present the first example of highly efficient platinum-catalyzed hydrosilylation of vinyl- and allylgermanes with different types of silsesquioxanes and spherosilicates. This protocol allows the straightforward introduction of organogermyl functionalities with alkyl chains linked to the silsesquioxane core with good yields and excellent selectivity. These derivatives may be applied as precursors for the development of advanced hybrid materials in the future. In addition, a comparison made between vinylsilanes and vinylgermanes showed a higher reactivity of germanium compounds in the hydrosilylation reaction. To the best of our knowledge, this is the first literature example of the functionalization of silsesquioxanes and spherosilicates with these types of germanium derivatives. The reaction parameters and kinetics were determined by in situ FT-IR. In addition, our research is supported by extensive data obtained from NMR measurements.

Synthesis of novel styryl-N-isopropyl-9H-carbazoles for designing trans-conjugated regular silicon hybrid materials.

An efficient synthesis and characterization of several new, conjugated styryl-carbazole compounds functionalized by monovinylsilanes in a stereocontrolled approach is presented. All N-organic derivatives were successfully examined in silylative coupling in the presence of ruthenium-hydride complexes 4 and 5. Furthermore, a novel class of vinylene-arylene linear oligomeric materials with 1,4-bis(dimethylvinylsilyl)naphthalene in the main chain was produced. Both reactions proceed very effectively, stereo- and regioselectively, allowing one to obtain E-isomer derivatives with high isolation yields.