Blue-to-Green Emitting Neutral Ir(III) Complexes Bearing Pentafluorosulfanyl Groups: A Combined Experimental and...

A structure-property relationship study of neutral heteroleptic (1 and 2, [Ir(C^∧N)₂(L^∧X)]) and homoleptic (3 and 4, fac-[Ir(C^∧N)₃]) Ir(III) complexes (where L^∧X = anionic 2,2,6,6-tetramethylheptane-3,5-dionato-κO³,κO⁶ (thd) and C^∧N = a cyclometalating ligand bearing a pentafluorosulfanyl (-SF₅) electron-withdrawing group (EWG) at the C₄ (HL1) and C₃ (HL2) positions of the phenyl moiety) is presented. These complexes have been fully structurally characterized, including by single-crystal X-ray diffraction, and their electrochemical and optical properties have also been extensively studied. While complexes 1 ([Ir(L1)₂(thd)]), 3 (Ir(L1)₃), and 4 (Ir(L2)₃) exhibit irreversible first reduction waves based on the pentafluorosulfanyl substituent in the range of -1.71 to -1.88 V (vs SCE), complex 2 ([Ir(L2)₂(thd)]) exhibits a quasi-reversible pyridine_C^∧N-based first reduction wave that is anodically shifted at -1.38 V. The metal + C^∧N ligand oxidation waves are all quasi-reversible in the range of 1.08-1.54 V (vs SCE). The optical gap, determined from the lowest energy absorption maxima, decreases from 4 to 2 to 3 to 1, and this trend is consistent with the Hammett behavior (σ_m/σ_p with respect to the metal-carbon bond) of the -SF₅ EWG. In degassed acetonitrile, for complexes 2-4, introduction of the -SF₅ group produced a blue-shifted emission (λ_em 484-506 nm) in comparison to reference complexes [Ir(ppy)₂(acac)] (R1, where acac = acetylacetonato) (λ_em 528 nm in MeCN), [Ir(CF₃-ppy) (acac)] (R3, where CF₃-ppyH = 2-(4-(trifluoromethyl)phenyl)pyridine) (λ_em 522 nm in DCM), and [Ir(CF₃-ppy)₃] (R8) (λ_em 507 nm in MeCN). The emission of complex 1, in contrast, was modestly red shifted (λ_em 534 nm). Complexes 2 and 4, where the -SF₅ EWG is substituted para to the Ir-C_C^∧N bond, are efficient phosphorescent emitters, with high photoluminescence quantum yields (Φ_PL = 58-79% in degassed MeCN solution) and microsecond emission lifetimes (τ_ε = 1.35-3.02 micros). Theoretical and experimental observations point toward excited states that are principally ligand centered (³LC) in nature, but with a minor metal-to-ligand charge-transfer (³MLCT) transition component, as a function of the regiochemistry of the pentafluorosulfanyl group. The ³LC character is predominant over the mixed ³CT character for complexes 1, 2, and 4, while in complex 3, there is exclusive ³LC character as demonstrated by unrestricted density functional theory (DFT) calculations. The short emission lifetimes and reasonable Φ_PL values in doped thin film (5 wt % in PMMA), particularly for 4, suggest that these neutral complexes would be attractive candidate emitters in organic light-emitting diodes.