Hofbeck, T. and Yersin, Hartmut (2010) The triplet state of fac-Ir(ppy)3. Inorganic Chemistry 49, pp. 9290-9299.
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The emitting triplet state of fac-Ir(ppy)₃ (fac-tris(2-phenylpyridine)iridium) is studied for the first time on the basis of highly resolved optical spectra in the rande of the electronic 0-0 transitions. For the compound dissolved in CH₂Cl₂ and cooled to cryogenic temperatures, three 0-0 transitions corresponding to the triplet substates I, II, and III are identified. They lie at 19693 cm⁻¹ (507.79 nm, I ―› 0), 19712 cm⁻¹ (507.31 nm, II ―› 0), and 19863 cm⁻¹ (503.45 nm, III ―› 0). From the large total zero-field splitting (ZFS) of 170 cm⁻¹, the assignment of the emitting triplet term as a ³MLCT state (metal-to-ligand charge transfer) is substantiated, and it is seen that spin-orbit couplings to higher lying ¹,³MLCT states are very effective. Moreover, the studies provide emission decay times for the three individual substates of τ(I) = 116 μs, τ(II) = 6.4 μs, and τ(III) = 200 ns. Further, group-theoretical considerations and investigations under application of high magnetic fields up to B = 12 T allow us to conclude that all three substates are non degenerate and that the symmetry of the complex in the CH₂Cl₂ matrix cage is lower than C₃. It follows that the triplet parent term is of ³A character. Studies of the emission decay time and photoluminescence quantum yield, φ(PL) of Ir(ppy)₃ in poly(methylmethacylate) (PMMA) in the temperature range of 1.5 =< T =< 370 K reveal average and individual radiative and nonradiative decay rates and quantum yields of the substates. In the range 80 =< T =< 370 K, φ(PL) is as high as almost 100 %. The quantum yield φ(PL) drops to ~88 % when cooled to T = 1.5 K. The investigations show further that the emission properties of Ir(ppy)₃ depend distinctly on the complex's environment or the matrix cage according to distinct charges of spin-orbit coupling effectiveness. These issues also have consequences for optimizations of the material's properties if applied as an organic light-emitting diode (OLED) emitter.
|Institutions:||Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Light and Matter) > Prof. Dr. Hartmut Yersin|
|Subjects:||500 Science > 540 Chemistry & allied sciences|
|Refereed:||Yes, this version has been refereed|
|Created at the University of Regensburg:||Yes|
|Owner:||Prof. Dr. Hartmut Yersin|
|Deposited On:||16 Dec 2010 06:04|
|Last Modified:||16 Dec 2010 06:04|