Mesyl and Triflyl Functionalized N-Heterocyclic Carbenes as Acceptor Fragments in Luminescent Carbene-Metal-Amide Complexes

Abstract

Synthetic procedures providing access to mesyl and triflyl functionalized derivatives of 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr) have been provided in detail. New luminescent carbene-metal-amide (CMA) Cu(I) complexes based on acceptor group functionalized SIPr have been prepared. The effect of the LUMO energy in the sulfonyl functionalized N-heterocyclic carbene (NHC) series on the emissive properties of the CMAs has been investigated.

Key words

N-heterocyclic carbenes - acceptor groups - carbene-metal-amides - copper(I) complexes - luminescence

Publication History

Received: 02 November 2022

Accepted after revision: 27 November 2022

Accepted Manuscript online:
27 November 2022

Article published online:
19 December 2022

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• 16 Compound 18a: A mixture of 1,3-bis(2,6-diisopropyl-4-(methylthio)phenyl)-4,5-dihydro-1H-imidazol-3-ium chloride (16a) (2.00 g, 3.43 mmol) and KHMDS (0.72 g, 3.61 mmol) in anhydrous THF (200 mL) was stirred for 1 h at r.t. Then CuCl (0.34 g, 3.43 mmol) was added and the mixture was stirred for additional 2.5 h at r.t. The formed precipitate containing product was separated by filtration. The solid was collected and purified using a Soxhlet apparatus (24 h, solvent: acetonitrile) to afford the product as a greenish solid. Yield: 1.34 g (60%). ¹H NMR (DMSO-d ₆, 500 MHz): δ = 7.88 (s, 4 H), 4.16 (s, 4 H), 3.36 (s, 6 H), 3.18 (hept, J = 6.7 Hz, 4 H), 1.38 (d, J = 6.7 Hz, 12 H), 1.31 (d, J = 6.7 Hz, 12 H). ¹³C NMR data not obtained due to the low solubility of compound 18a.
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• 18 Compound 18b: A mixture of 1,3-bis(2,6-diisopropyl-4-((trifluoromethyl)sulfonyl)phenyl)-4,5-dihydro-1H-imidazol-3-ium chloride (17b) (2.16 g, 3.13 mmol), CuCl (0.38 g, 3.84 mmol) and K₂CO₃ (0.70 g, 5.06 mmol) in acetone (200 mL) was stirred and heated at reflux for 24 h. The precipitate containing product was separated by filtration, washed with H₂O and dried at r.t. The solid was purified by using a Soxhlet apparatus (48 h, solvent: acetonitrile) to afford the product as a greenish solid. Yield: 1.72 g (73%). ¹H NMR (DMSO-d ₆, 500 MHz): δ = 8.03 (s, 2 H), 4.25 (s, 4 H), 3.24–3.20 (m, 4 H), 1.38 (d, J = 6.8 Hz, 12 H), 1.31 (d, J = 6.8 Hz, 12 H). ¹³C NMR data not obtained due to the low solubility of compound 18b. ¹⁹F NMR (DMSO-d ₆, 471 MHz): δ = –78.26.
• 19 Compound 19a: To a solution of 9H-carbazole (0.093 g, 0.556 mmol) in anhydrous degassed THF (45 mL), KOtBu (0.063 g, 0.561 mmol) was added and the mixture was stirred at r.t. for 30 min. Then compound 18a (0.300 g, 0.465 mmol) was added and the mixture was stirred for an additional 3 h. Then mixture was filtered via syringe filter into anhydrous degassed hexane (250 mL) to precipitate the product. The obtained mixture was filtered and washed with hexane (50 mL) to obtain the product as an off-white solid. Yield: 0.234 g (65%). ¹H NMR (DMSO-d ₆, 500 MHz): δ = 8.04 (s, 4 H), 7.76 (d, J = 7.5 Hz, 2 H), 6.83 (t, J = 7.5 Hz, 2 H), 6.73 (t, J = 7.3 Hz, 2 H), 5.83 (d, J = 8.1 Hz, 2 H), 4.36 (s, 4 H), 3.43 (s, 6 H), 3.35 (m, 4 H), 1.42 (d, J = 6.7 Hz, 12 H), 1.27 (d, J = 6.7 Hz, 12 H). ¹³C NMR (DMSO-d ₆, 125.77 MHz): δ = 202.70, 149.15, 148.86, 142.41, 138.90, 123.32, 123.24, 123.03, 118.98, 115.15, 112.99, 53.56, 43.17, 28.59, 24.63, 23.19. A similar method was used for the synthesis of compounds 19b and 20a (see the Supporting Information).
• 20 CCDC 2214035 (19a) and 2214034 (20a) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures