Triplet Excited States Modulated by Push-Pull Substituents in Monocyclometalated Iridium(III) Photosensitizers

A series of novel monocyclometalated [Ir(tpy)(btp)Cl]⁺ complexes (Ir2-Ir5) were synthesized using 2,2':6',2″-terpyridine (tpy) and 2-(2-pyridyl)benzo[b]thiophene (btp) ligands, as well as their derivatives bearing electron-donating tert-butyl (t-Bu) and electron-withdrawing trifluoromethyl (CF₃) groups. Ir2-Ir5 exhibited visible-light absorption stronger than that of the known complex [Ir(tpy)(ppy)Cl]⁺ (Ir1; ppy = 2-phenylpyridine). Spectroscopic and computational studies revealed that two triplet states were involved in the excited-state dynamics. One is a weakly emissive and short-lived ligand to ligand charge-transfer (LLCT) state originating from the charge transfer from the btp to the tpy ligand. The other is a highly emissive and long-lived ligand-centered (LC) state localized on the btp ligand. Interestingly, the excited state dominant with ³LLCT was completely changed to the ³LC state upon the introduction of substituents on both the tpy and btp ligands. For instance, the excited state of the parent complex Ir2 was weakly emissive (Φ = 2%) and short-lived (τ = 110 ns) in CH₂Cl₂; conversely, Ir5, fully furnished with t-Bu and CF₃ groups, displayed intense phosphorescence with a prolonged lifetime (τ = 14 μs). This difference became increasingly prominent when the solvent was changed to aqueous CH₃CN, most probably due to the ³LLCT stabilization. The predominant excited-state nature was switchable between the ³LLCT and ³LC states depending on the substituents employed; this was demonstrated through investigations of Ir3 and Ir4, bearing either the t-Bu or the CF₃ group, where the complexes exhibited properties intermediate between those of Ir2 and Ir5. All of the Ir(III) complexes were tested as photosensitizers in photocatalytic H₂ evolution over a Co molecular catalyst, and Ir5 outperformed the others, including Ir1, due to improvement in the following key properties: visible-light-absorption ability, excited-state lifetime, and reductive power of the one-electron-reduced species against the catalyst.