Synthesis of Copper(I) Cyclic (Alkyl)(Amino)Carbene Complexes with Potentially Bidentate N^N, N^S and S^S Ligands for Efficient White Photoluminescence

Romanov, Alexander, Chotard, Florian, Rashid, Jahan and Bochmann, Manfred (2019) Synthesis of Copper(I) Cyclic (Alkyl)(Amino)Carbene Complexes with Potentially Bidentate N^N, N^S and S^S Ligands for Efficient White Photoluminescence. Dalton Transactions, 48. pp. 15445-15454. ISSN 1477-9226

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Abstract

The reaction of (Me2L)CuCl with either NaS2CX [X = OEt, NEt2 or carbazolate (Cz)] or with 1,3-diarylguanidine, 1,3-diarylformamidine or thioacetaniline in the presence of KOtBu affords the corresponding S- or N-bound copper complexes (Me2L)Cu(S^S) 1–3, (Me2L)Cu(N^N) 4/5 and (Me2L)Cu(N^S) 6 (aryl = 2,6-diisopropylphenyl; Me2L = 2,6-bis(isopropyl)phenyl-3,3,5,5-tetramethyl-2-pyrrolidinylidene). The crystal structure of (Me2L)Cu(S2CCz) (3) confirmed the three-coordinate geometry with S^S chelation and perpendicular orientation of the carbene and S^S ligands. On heating 3 cleanly eliminates CS2 and forms (Me2L)CuCz. The N-bound complexes show strongly distorted T-shaped (4) or undistorted linear (5) geometries. On excitation with UV light the S-bound complexes proved non-emissive, while the guanidinato and formamidinato complexes are strongly phosphorescent, with excited state lifetimes in the range of 11–24 µs in the solid state. The conformationally flexible formamidinato complex 5 shows intense green-white phosphorescence with a solid-state quantum yield of >96%.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: LivePure Connector
Date Deposited: 17 Jun 2019 10:30
Last Modified: 20 Sep 2020 23:58
URI: https://ueaeprints.uea.ac.uk/id/eprint/71409
DOI: 10.1039/C9DT02036E

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