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Heteroleptic C^N cyclometalated iridium(III) complexes incorporating a monostyryl/distyryl BODIPY ligand via acetylide bonds of 2,2′-bipyridine (bpy) with both absorption (ca. ε = 8.96 × 104 M−1 cm−1, 9.89 × 104 M−1 cm−1, and 7.89 × 104 M−1 cm−1 at 664 nm, 644 nm, and 729 nm for Ir-2, Ir-3 and Ir-4, respectively) and fluorescence emission bands (ca. 624–794 nm for Ir-1, Ir-2, Ir-3 and Ir-4) in the near infra-red region (NIR) and exceptionally long-lived triplet excited states (τ = 156.5 μs for Ir-2) have been reported. Ir(ppy)3 (Ir-0; ppy = 2-phenylpyridine) was used as reference, which gives the typical weak absorption in visible range (ε = 1.51 × 104 M−1 cm−1 M−1 cm−1 at 385 nm). The nanosecond time-resolved transient absorption and DFT calculations proposed that styryl BODIPY-localized long lived 3IL states were populated for Ir-1, Ir-2, Ir-3 and Ir-4 (τT = 106.6 μs, 156.5 μs, 92.5 μs and 31.4 μs, respectively …