Triplet states, ligand luminescence

Specific examples are now used to demonstrate these concepts. First, consider the group Ru(bpy)j2+ (luminescent), Os(bpy)32+ (slightly luminescent), and Fe(bpy)32+ (nonluminescent) (Table4.1). For Fe(bpy)32+, despite an exhaustive search no emission has ever been detected even at 77K we routinely use it as a nonemissive solution filter. All three iso structural eft systems are in the same oxidation state with the same electronic configuration (ft6). The Fe(II) complex has an intense MLCT band at 510 nm, and the Ru(II) complex at 450 nm the Os(II) complex has intense MLCT bands that stretch out to 700 nm. The n-n transitions are all quite similar in all three complexes with intense absorptions around 290 nm and ligand triplet states at 450 nm (inferred from the free ligand and other emissive complexes and the insensitivity of these states to coordination to different metals). 

Lastly, photochemically unstable ligands should be avoided. Re(bpy)(CO)3Cl shows a moderately efficient MLCT emission at room temperature (R. M. Ballew, unpublished results from our laboratory). However, the apparently closely related Re(dpk)(CO)3Cl (dpk = 2,2 -dipyridyl ketone) shows a benzophenone like phosphorescence at 77K indicating that the n-n excited state of the ketone in complex is the lowest state of the complex. No luminescence is seen at room temperature, and even at 77K the dpk triplet state is such a powerful hydrogen atom extractor that it removes protons from alcohol glasses as seen by the formation of the intense blue color of the keto free radical. The absence of an MLCT emission is caused by the greater difficulty of reducing dpk relative to bpy, which pushes the MLCT states above the dpk ligand states. 

Spectroscopic properties of [Ru(bpy)3] " ", and the effects of varying the diimine ligands in [Ru(bpy)3 L ] + (L = diimine) on the electronic spectra and redox properties of these complexes have been reviewed. The properties of the optical emission and excitation spectra of [Ru(bpy)3] +, [Ru(bpy)2(bpy-d )] + and [Ru(bpy-d )3] " " and of related Os, Rh , and Pt and Os species have been analyzed and trends arising from changes in the metal d or MLCT character in the lowest triplet states have been discussed. A study of the interligand electron transfer and transition state dynamics in [Ru(bpy)3] " " has been carried out. The results of X-ray excited optical luminescence and XANES studies on a fine powder film of [Ru(bpy)3][C104]2 show that C and Ru localized excitation enhances the photoluminescence yield, but that of N does not. 

The europium complexes are highly luminescent, with quantum yields of up to 0.19 in methanol. The ligand triplet state is too low in energy to efficiently populate the terbium excited state, and no metal-centered emission is observed. 

Latva, M. Takalo, H. Mukkala, V.- . Matachescu, C. Rodrfguez-Ubis, J.-C. Kankare, J. Correlation between the lowest triplet state energy level of the ligand and lanthanide(III) luminescence quantum yield. J. Luminesc. 1997, 75, 149-169. 

If the Crosby model does not hold, then luminescence properties should be dictated by the individual chromophores in that molecule i.e., weak ligand-ligand interaction would leave a set of individual k states. Once a triplet state on one ligand is populated, transfer to states of other ligands should be poor1461 this raises the possibility of multiple emissions. 

Fig. 5. The Eu(III) luminescence quantum yields of Eu(III) chelates as a function of the lowest triplet state energy of the ligand. Redrawn, with permission, after Latva et al. (1997).

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