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Evidence for strong mixing between the LC and MLCT excited states in bis(2-phenylpyridinato-C2,N')(2,2'-bipyridine)iridium(III)

Colombo, Mirco G.
Guedel, Hans U.
Published in Inorganic Chemistry. 1993, vol. 32, no. 14, p. 3088 - 3092
Abstract The well-resolved absorption, excitation, and luminescence spectra of [Ir(ppy)2bpy]+ (ppyH = 2-phenylpyridine, bpy = 2,2'-bipyridine) in different media at cryogenic temperatures are presented. In solutions and glasses at ambient temperature the lowest energy excited state corresponds to an Ir - bpy charge-transfer excitation whereas in the crystalline host lattice [Rh(ppy)2bpy]PF6 the lowest excited state at 21 450 cm-1 is assigned to a 37r-r* excitation localized on the cyclometalating ppy- ligands. The next higher excited Ir - bpy charge-transfer state has shifted to 21 820 cm-', only 300 cm-I above the 3LC excited state. The close proximity of the 3LC and 3MLCT excited states and the large spin-orbit coupling constant of Ir3+ induce a strong mixing of charge-transfer character into the 3LC lowest excited states, resulting in increased oscillator strengths, reduced lifetimes, short axis polarized transitions, and a large zero-field splitting of 10-15 cm-1.
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COLOMBO, Mirco G., HAUSER, Andreas, GUEDEL, Hans U. Evidence for strong mixing between the LC and MLCT excited states in bis(2-phenylpyridinato-C2,N')(2,2'-bipyridine)iridium(III). In: Inorganic Chemistry, 1993, vol. 32, n° 14, p. 3088 - 3092.

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