Photochemistry and Photophysics of Coordination Compounds

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228 M.T. Indelli et al. The dyads generically indicated in Eqs. 6–8 are actually heterobinuclear complexes when, as it is often the case, the photosensitizer P or the quencher Q are transition metal complex moieties, and the chemical linkage is provided by a bridging ligand. A number of examples of such processes are discussed in the following sections. 3.2.1 Photoinduced Electron Transfer in Ru(II)-Rh(III) Polypyridine Dyads Though not exclusively, dyads containing Rh(III) polypyridine units have often involved as P or Q (Eqs. 7, 8) the chromophores par excellence of inorganic photochemistry, namely Ru(II) polypyridine complexes. The general behavior of Ru(II)-Rh(III) polypyridine dyads can be discussed taking dyad 15 as an example [84]. The absorption spectrum of dyad 15, as compared with those of the Ru(Me2phen)2(Me2bpy) 2+ and Rh(Me2bpy)3 3+ molecular components, is shown in Fig. 5. It shows that the spectra of the molecular components are strictly additive, as expected for weak intercomponent interaction, and that selective (100%) excitation of the Ru(II) chromophore can be easily performed in the visible region, whereas partial excitation of the Rh(III) component (ca. 70% at300 nm) can be achieved in the ultraviolet. The energy level diagram for this dyad (Fig. 6) shows that, besides the photophysical processes taking place within each molecular component, a number of intercomponent processes are thermodynamically allowed. They include: ∗Ru(II)-Rh(III) → Ru(III)-Rh(II) electron transfer from excited Ru(II) (a) Ru(II)-∗Rh(III) → Ru(III)-Rh(II) electron transfer to excited Rh(III) (b) Ru(II)-∗Rh(III) → ∗Ru(II)-Rh(III) energy transfer from Rh(III) to Ru(II) (c) Ru(III)-Rh(II) → Ru(II)-Rh(III) back electron transfer . (d)
Photochemistry and Photophysics of Coordination Compounds: Rhodium 229 Fig. 5 Absorption spectra of the Ru(II)-Rh(III) dyad 15 (dotted line, c), and of the Ru(Me2phen)2(Me2bpy) 2+ (dashed line, b) andRh(Me2bpy)3 3+ (continuous line, a) molecular components Fig. 6 Energy level diagram and photophysical processes for the Ru(II)-Rh(III) dyad 15 For dyad 15, all these processes could be time-resolved by nanosecond and picosecond techniques under the appropriate experimental conditions (visible excitation for a, UV excitation for b and d, rigid matrix for c), leading to the
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280 Topics in Current Chemistry Edi
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Photochemistry and Photophysics of
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X Preface nation Compounds. The ven
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