Compound 1

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Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

The polypyridyl ligand 4′-p-tolyl-2,2′:6,2″-terpyridine (ttpy) was prepared as described by Wand and Hana. [Ir(ttpy)Cl₃] was prepared based on the procedure reported by Porras et al (Porras, J. A. Mills, I. N. Transue, W. J. & Bernhard, S. Highly fluorinated Ir(III)–2, 2′: 6′, 2″-terpyridine–phenylpyridine–X complexes via selective C–F activation: robust photocatalysts for solar fuel generation and photoredox catalysis. J. Am. Chem. Soc. 138, 9460-9472 (2016). A mixture of [Ir(ttpy)Cl₃] (125 mg, 0.20 mmol) and excess 3-phenylisoquinoline (3-pq) (82 mg, 0.40 mmol) in glycol (10 mL) was stirred overnight at 453 K under nitrogen. The reaction mixture became a clear orange solution. After cooling to room temperature, the solution was poured into 50 mL saturated NH₄PF₆ solution to give an orange precipitate. The precipitate was isolated by filtration and washed with water and diethyl ether 3 times. The crude product was purified by column chromatography on neutral alumina oxide with methanol−dichloromethane (1:9 v/v) as the eluent. The solvent was removed under reduced pressure, and orange complex 1 was obtained. Yield: 45%. ESI-MS [CH₃OH, m/z]: 755.5 ([M-PF₆]⁺) Anal. calcd. for IrC₃₇H₂₇N₄ClPF₆: C, 49.36; H, 3.02; N, 6.22; found: C, 49.25; H, 3.09; N, 6.24. ¹H NMR (400 MHz, d₆-(CD₃)₂SO) δ 10.66 (s, 1H), 9.28 (s, 2H), 9.00 (d, J = 9.6 Hz, 2H), 8.99 (s, 1H), 8.45 (d, J = 8.2 Hz, 1H), 8.31 (d, J = 8.4 Hz, 1H), 8.28 (d, J = 8.2 Hz, 2H), 8.23 (t, J = 8.0 Hz, 2H), 8.05 (t, J = 7.6 Hz, 1H), 8.00 (d, J = 7.6 Hz, 1H), 7.89 (t, J = 7.6 Hz, 1H), 7.81 (d, J = 5.4 Hz, 2H), 7.57 (d, J = 8.0 Hz, 2H), 7.48 (t, J = 6.4 Hz, 2H), 6.96 (t, J = 7.6 Hz, 1H), 6.75 (t, J = 7.2 Hz, 1H), 6.08 (d, J = 7.6 Hz, 1H), 2.50 (s, 3H). ¹³C NMR (101 MHz, DMSO) δ 158.39, 157.90, 155.79, 155.40, 152.47, 151.74, 144.23, 141.83, 140.52, 139.72, 137.36, 134.07, 132.80, 130.62, 130.44, 129.82, 129.61, 129.43, 128.91, 128.57, 128.49, 127.48, 126.43, 124.51, 124.34, 121.61, 117.49, 21.45.