Dynamics of the Excited States of [Ir(ppy)2bpy]+ with Triple Phosphorescence
We investigated the relaxation dynamics of bis(2-phenylpyridinato-)(2,2′-bipyridine)iridium(III), [Ir(ppy)2bpy]+ using the technique of time-resolved spectroscopy. In the visible emission spectra this molecule exhibits triple phosphorescence: displaying blue, green, and orange bands. From the depend...
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Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2010-09, Vol.114 (38), p.10339-10344 |
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Sprache: | eng |
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Zusammenfassung: | We investigated the relaxation dynamics of bis(2-phenylpyridinato-)(2,2′-bipyridine)iridium(III), [Ir(ppy)2bpy]+ using the technique of time-resolved spectroscopy. In the visible emission spectra this molecule exhibits triple phosphorescence: displaying blue, green, and orange bands. From the dependence of spectral shifts with polarity of solvent, decay lifetimes, and the results of calculations using time-dependent density functional theory, we assigned these three emitting states to be triplet interligand charge-transfer (3LLCT), metal-to-ligand ppy charge transfer (3MLCTppy), and metal-to-ligand bpy charge transfer (3MLCTbpy) states. The blue states were formed promptly after excitation at wavelength 355 nm; the one lying at higher energy decaying with a time coefficient 0.79−2.56 ns is assigned to be a triplet MLCT, and the other at lower energy decaying in 1.5−2.8 μs is assigned to 3LLCT(A), A symmetry. This decay time coefficient of 3LLCT(A) decreases with increasing dielectric constant of the solvent indicating this state mixing of some MLCT character. The green state 3MLCTppy decays in 0.13−4.8 ns to a nearby intermediate state either 3MLCTppy or 3MLCTbpy. The orange state 3MLCTbpy is coupled to the intermediate state to have a rise time about 0.36−0.84 ns and decays in 425−617 ns. Although many triplet states exist in a small energy range, they couple weakly to display triple emission. All 3LLCT and 3MCLT states are coupled to the singlet 1LLCT manifold directly and/or indirectly and contribute to the emission in the visible range. |
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ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/jp102264q |