One-pot three-step thioconjugate addition-oxidation-Diels–Alder reactions of ethyl propiolate

Ethyl propiolate undergoes one-pot three-step thioconjugate addition-oxidation-Diels–Alder cycloaddition when treated with a variety of thiols in the presence of catalytic base, meta-chloroperbenzoic acid, lithium perchlorate, and cyclopentadiene. The reaction of S‑aryl thiols is catalyzed by trialkylamines, and the reaction of aliphatic thiols requires catalytic alkoxide base. Yields of the major diastereomer of the conveniently functionalized bicyclic products range from 47 to 81% depending upon the thiol reactant, which compares favorably to yields observed when the entire synthesis is performed step by step

Identification of the key parameters for horizontal transition dipole orientation in fluorescent and TADF organic light-emitting diodes

This research was financially supported by the Volkswagen Foundation (No. 93404), the European Commission under EU Horizon 2020 Grant Agreement No. 812872 (TADFlife), the European Research Council under the European Union's Horizon 2020 Framework Programme (FP/2014-2020)/ERC grant agreement no. 640012 (ABLASE), and The Leverhulme Trust (RPG-2016047). M.C.G. acknowledges support from the Alexander von Humboldt Stiftung through the Humboldt-Professorship. All computations were performed using resources kindly provided by the University of Mons (UMONS), supported by the Belgian National Fund for Scientific Research (FRS-FNRS). Computational resources were provided by the Consortium des Équipements de Calcul Intensif (CÉCI) funded by F.R.S.-FNRS under Grant 2.5020.11. Y.O. acknowledges funding from the FRS-FNRS under the grant F.4534.21 (MIS-IMAGINE).In organic light-emitting diodes (OLEDs), horizontal orientation of the emissive transition dipole moment (TDM) can improve light outcoupling efficiency by up to 50% relative to random orientation. Therefore, there have been extensive efforts to identify drivers of horizontal orientation. The aspect ratio of the emitter molecule and the glass-transition temperature (Tg) of the films are currently regarded as particularly important. However, there remains a paucity of systematic studies that establish the extent to which these and other parameters control orientation in the wide range of emitter systems relevant for state-of-the-art OLEDs. Here, recent work on molecular orientation of fluorescent and thermally activated delayed fluorescent emitters in vacuum-processed OLEDs is reviewed. Additionally, to identify parameters linked to TDM orientation, a meta-analysis of 203 published emitter systems is conducted and combined with density-functional theory calculations. Molecular weight (MW) and linearity are identified as key parameters in neat systems. In host–guest systems with low-MW emitters, orientation is mostly influenced by the host Tg, whereas the length and MW of the emitter become more relevant for systems involving higher-MW emitters. To close, a perspective of where the field must advance to establish a comprehensive model of molecular orientation is given.Publisher PDFPeer reviewe

One-pot synthesis of (Z)-B-sulfonyl enoates from ethyl propiolate

B-Sulfonyl enoates may be synthesized through a one-pot two-step sequence from ethyl propiolate with good to excellent selectivity for the Z isomer. Trialkylamines catalyze thioconjugate additions of aryl thiols, and alkoxides catalyze the addition of aliphatic thiols. Addition of meta-chloroperbenzoic acid (mCPBA) and LiClO4 to the reaction mixture provides rapid access to the sulfonyl enoates. Yields of the pure Z isomer range from 51 – 90%