title: Controlling the excited state and photosensitizing property of a 2-(2-pyridyl)benzo[b]thiophene-based cationic iridium complex through simple chemical modification.
abstract: Bis-cyclometalated cationic iridium (Ir) complexes 1-4 comprising two 2-(2-pyridyl)benzo[b]thiophene (btp) ligands and one 2,2'-bipyridyl (bpy) ancillary ligand with different substituents were prepared as new visible light-absorbing sensitizers and examined for their photophysical and electrochemical properties. Complex 1 was prepared as a parent complex without any substituents. Complexes 2-4 contained methyl-, methoxy-, and trifluoromethyl groups at 4,4'-positions on the bpy ancillary ligand. Systematic investigation of these complexes revealed that such a simple chemical modification selectively controls the excited-state lifetime, while the absorption and emission spectral features remain unchanged. Specifically, the phosphorescence lifetimes of complexes 2 and 3 with electron-donating groups (τ = 3.50 μs, 3.90 μs) were found to be much longer than that of complex 1 (τ = 0.273 μs), and complex 4, possessing strong electron-withdrawing trifluoromethyl groups, did not exhibit detectable phosphorescence at room temperature. The large differences in excited-state lifetimes of complexes 1-3, as well as the nonemissive character of complex 4, are attributed to a strong influence of the substituents on the ligand field strength. The increased σ-donating ability of the ancillary ligand in complexes 2 and 3 destabilizes a short-lived, nonemissive triplet metal-centered ((3)MC) state and increases the energy separation between the (3)MC state and emissive triplet ligand-centered ((3)LC) state based on the btp ligand. For complex 4, however, the (3)MC state is close in energy to the (3)LC state because of the decreased σ-donating ability of the ancillary ligand. Additional evidence of the (3)MC state associated with the changeable excited state was also provided via low-temperature phosphorescence measurements and density functional theory calculations. Ir complexes 1-4 were tested as sensitizers in photoinduced electron-transfer reaction of triethanolamine and methylviologen chloride (MVCl2). As a result, complexes 2 and 3 exhibited much better photosensitizing property compared to complex 1 since their long-lived excited states promoted an oxidative quenching pathway. This Study has first demonstrated that simple substitution on the diimine ancillary ligand can control the (3)MC state of the bis-cyclometalated cationic Ir complex to finely tune the excited-state lifetime and photosensitizing property.
authors.affiliation: Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo , 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan.
authors.forename: Shin-ya
authors.initials: SY
authors.lastname: Takizawa
authors.forename: Kengo
authors.initials: K
authors.lastname: Shimada
authors.forename: Yoichi
authors.initials: Y
authors.lastname: Sato
authors.forename: Shigeru
authors.initials: S
authors.lastname: Murata
mesh_terms: D002412:Cations; D007495:Iridium / Q000737:chemistry*; D017319:Photosensitizing Agents / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013876:Thiophenes / Q000737:chemistry*
chemical_list: D002412:Cations; D017319:Photosensitizing Agents; D013876:Thiophenes; D007495:Iridium