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Organic Donor–Acceptor Thermally Activated Delayed Fluorescence Photocatalysts in the Photoinduced Dehalogenation of Aryl Halides

Megan Bryden, Ettore Crovini, Thomas Comerford, Armido Studer, Eli Zysman‐Colman

2024Angewandte Chemie International Edition15 citationsDOIOpen Access PDF

Abstract

Abstract We report a family of donor‐acceptor thermally activated delayed fluorescent (TADF) compounds based on derivatives of DMAC‐TRZ , that are strongly photoreducing. Both E ox and thus E * ox could be tuned via substitution of the DMAC donor with a Hammett series of p ‐substituted phenyl moieties while E red remained effectively constant. These compounds were assessed in the photoinduced dehalogenation of aryl halides, and analogues bearing electron withdrawing groups were found to produce the highest yields. Substrates of up to E red =−2.72 V could be dehalogenated at low PC loading (1 mol %) and under air, conditions much milder than previously reported for this reaction. Spectroscopic and chemical studies demonstrate that all PCs, including literature reference PCs, photodegrade, and that it is these photodegradation products that are responsible for the reactivity.

Topics & Concepts

HalogenationPhotochemistryArylAcceptorHalideFluorescenceChemistryOrganic chemistryAlkylPhysicsQuantum mechanicsCondensed matter physicsRadical Photochemical ReactionsSulfur-Based Synthesis TechniquesCatalytic C–H Functionalization Methods
Organic Donor–Acceptor Thermally Activated Delayed Fluorescence Photocatalysts in the Photoinduced Dehalogenation of Aryl Halides | Litcius