Photochemistry and Photophysics of Coordination Compounds

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230 M.T. Indelli et al. detailed kinetic picture of Fig. 6 [84]. The widely different rates of the three ET processes (a, b, d) can be rationalized in terms of predominant driving force effects [84], as shown schematically in Fig. 7. Fig. 7 Free-energy correlation of rate constants for the three electron transfer processes of dyad 15 Since most Ru(II)-Rh(III) polypyridine dyads have very similar energetics, the qualitative features illustrated above for dyad 15 can be safely generalized to this whole class of compounds. For example, in dyad 16 [85]therateconstants of processes a, b,andd are slower by a factor of ca. 3 but have the same relative magnitudes as for dyad 15. The slower rates are likely related to the longer aliphatic bridge, although for this and related [86] dyads, the flexibility of the bridges limits the validity of such comparisons. Within this general type of behavior of Ru(II)-Rh(III) dyads, a number of experimental studies have been specifically aimed at investigating the role of the bridge in determining electron transfer rates. As has been the case for other types of bimetallic dyads [87–90], particular attention has been devoted to Ru(II)-Rh(III) dyads with modular bridges involving p-phenylene spacer units [6, 91, 92]. The dyads in Chart 1 provide a homogeneous series
Photochemistry and Photophysics of Coordination Compounds: Rhodium 231 with appreciably constant energetics but differing in the number (1–3) of p-phenylene spacers in the bridge and, in one of the two dyads with three spacers, for the presence of alkyl substituents on the central spacer. Upon excitation of the Ru(II)-based chromophore, the rate constants of photoinduced electron transfer (process a in the above general scheme) have been measured by time-resolved emission and transient absorption techniques in the nanosecond and picosecond time domains [6, 92]. The values for Ru-ph- Rh, Ru-ph2-Rh, andRu-ph3-Rh (Chart 1), when plotted as a function of the metal–metal distance r (Fig. 8), display an exponential decrease (Eq. 9): k = k(0) exp(– βr). (9) Chart 1
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280 Topics in Current Chemistry Edi
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Photochemistry and Photophysics of
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Volume Editors Prof. Vincenzo Balza
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Topics in Current Chemistry Also Av
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X Preface nation Compounds. The ven
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Contents Photochemistry and Photoph
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Page 279 and 280: Subject Index Alkyne bridges 148 An
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