Blue emissive cobalt(III) complexes and their use in the photocatalytic trifluoromethylation of polycyclic aromatic hydrocarbons
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The first examples of room temperature (r.t.) luminescent Co(III) complexes ( 1 and 2 ) are presented that exhibit intense ligand‐to‐metal and ligand‐to‐ligand charge transfer absorption in the low energy UV region (λabs ~ 360‐400 nm) and low‐negative quasi‐reversible reduction events (E1/2(red) = −0.58 V and −0.39 V vs. SCE for 1 and 2 , respectively). The blue emission of 1 and 2 at r.t. is due to the large bite angles and strong σ‐donation of the ligands, the combined effect of which helps to separate the emissive 3LMCT (triplet ligand‐to‐metal charge transfer) and the non‐emissive 3MC (triplet metal‐centered) states. 1 and 2 were found to be powerful photo‐oxidants (ECo(III)*/Co(II) = 2.26 V and 2.75 V vs. SCE of 1 and 2 , respectively) and were used as inexpensive photoredox catalysts for the regioselective mono(trifluoromethylation) of polycyclic aromatic hydrocarbons (PAHs) in good yields (~ 40‐58%).
Pal , A K , Li , C , Hanan , G S & Zysman-Colman , E 2018 , ' Blue emissive cobalt(III) complexes and their use in the photocatalytic trifluoromethylation of polycyclic aromatic hydrocarbons ' , Angewandte Chemie International Edition , vol. 57 , no. 27 , pp. 8027-8031 . https://doi.org/10.1002/anie.201802532
Angewandte Chemie International Edition
© 2018 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1002/anie.201802532
DescriptionA.K.P and G.S.H thank Natural Sciences and Engineering Research Council of Canada. A.K.P thanks the Leverhulme Trust Early Career Fellowship (ECF-2017-326) and the University of St Andrews. The authors thank the Prof. & Mrs Purdie Bequests Scholarship and AstraZeneca support for C.L. EZ-C thanks the Engineering and Physical Sciences Research Council (EP/M02105X/1) and the University of St Andrews.
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