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Interligand electron transfer

Fig. 7. Excited-state interligand electron transfer in fac-[Re(MQ)(CO)3(dmb)]2+. Reproduced from Ref. (15) by permission of the Royal Society of Chemistry. Fig. 7. Excited-state interligand electron transfer in fac-[Re(MQ)(CO)3(dmb)]2+. Reproduced from Ref. (15) by permission of the Royal Society of Chemistry.
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. [Pg.575]

Experimental data for the interligand electron transfer kinetics following photoexcitation of [Os(bpy)3] " " are in agreement with a reaction/diffusion model measurements were made in a range of solvents. The variable parameters in the model are interligand electronic coupling and solvent polarization barrier height. [Pg.582]

TRIR and TR3 spectra were used to study the dynamics and mechanism of metal-to-ligand and interligand electron transfer in /uc-[Re(-MQ+)(CO)3(dmb)]2+, where MQ+ = V-methyl-4,4 -bipyridinium, dmb = 4,4,-dimethyl-2,2,-bipyridine.191,192... [Pg.313]

Benko G., Kallioinen J., Myllyperkio P., Trif F., Korppi-Tommola J. E. I., Yartsev A. P. and Sundstrom V. (2004), Interligand electron transfer determines triplet excited state electron injection in RuN3-sensitized TiOi films , J. Phys. Chem. B 108, 2862-2867. [Pg.662]

Doom and Hupp have used preresonance Raman spectra in an analysis of the vibronic components which contribute to the intervalence absorption maximum of [(CN)5Ru -CN-Ru (NH3)5] and to the MLCT absorption maximum of [(bpy)Ru(NH3)4] ". These authors employ the time-dependent scattering approach of Heller to obtain the nuclear displacements of several vibrational modes coupled to the electronic transitions. They find in each case that several vibrational modes, spanning a wide range of frequencies, do contribute significantly to the photoinduced electron transfer processes. Hopkins and co-workers have used a two-color, ps Raman technique to investigate interligand electron transfer in Ru(II)-tn5-polypyridyl complexes, and they find vibrational relaxation of the electronically excited mole ule occurs within about 30 ps of excitation, after which interligand equilibration occurs more slowly than 5 x 10 s. [Pg.14]

In what follows we will summarize the results that lead to the conclusion that electron transfer between the pyridyl ligands of the RuN3 sensitizer (interligand electron transfer, ILET) is the rate-limiting process... [Pg.170]

In conclusion, photoinduced electron transfer fi om the sensitizer RuN3 to nanostructured Ti02 occurs along two pathways. The major part of the molecules ( 60 %) inject directly fiom the non-thermalized MLCT state prior to IVR and intersystem crossing, while the remaining part inject from the thermalized triplet state of the non-attached ligand, in a process controlled by interligand electron transfer. [Pg.176]

Malone, R.A., Kelley, D.F. Interligand electron transfer and transition state dynamics in Ru (Il)trisbipyridine. J. Chem. Phys. 95, 8970-8976 (1991)... [Pg.221]

In order to explain this increase in electron transfer rate and to elucidate which pathway was followed (intraligand or interligand), a rotaxane structure was elaborated171,721 (Figure 6). Here, the principle of construction of the architecture was again based on the 3-dimensional template effect of copper (i). [Pg.255]


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