http://www.cnr.it/ontology/cnr/individuo/prodotto/ID50989
Photoinduced Electron Transfer across Oligo-Paraphenylene Bridges. Distance and Conformational Effects in Ru(II)-Rh(III) Dyads (Articolo in rivista)
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- Photoinduced Electron Transfer across Oligo-Paraphenylene Bridges. Distance and Conformational Effects in Ru(II)-Rh(III) Dyads (Articolo in rivista) (literal)
- Anno
- 2007-01-01T00:00:00+01:00 (literal)
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- Indelli M. T.; Chiorboli C.; Flamigni L.; De Cola L.; Scandola F. (literal)
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- In: Inorganic Chemistry, vol. 46 (14) pp. 5630 - 5641. ACS Publications, 2007. (literal)
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- ISI Web of Science (WOS) (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
- Dipartimento di Chimica, Università di Ferrara, 44100 Ferrara, Italy, ISOF-CNR (Sezione di Ferrara), 44100 Ferrara, Italy, ISOF-CNR, 40129 Bologna, Italy, Physikalisches Institut, Westfälische Wilhelms-Universität Münster, D-48149 Münster, Germany, and INSTM (UdR Ferrara), 44100 Ferrara, Italy (literal)
- Titolo
- Photoinduced Electron Transfer across Oligo-Paraphenylene Bridges. Distance and Conformational Effects in Ru(II)-Rh(III) Dyads (literal)
- Abstract
- A series of rodlike ruthenium(II)-rhodium(III) polypyridine dyads based on modular oligo-p-phenylene bridges, of the general formula [(Me2phen)2Ru-bpy-(ph)n-bpy-Rh(Me2bpy)]5+ (Me2phen = 4,7-dimethyl-1,10-phenanthroline; bpy = 2,2'-bipyridine; ph = 1,4-phenylene; n = 1-3), have been synthesized and their photophysical properties investigated. The dyad [(Me2bpy)2Ru-bpy-(ph)3'-bpy-Rh(Me2bpy)]5+ with the central phenylene unit bearing two hexyl chains has also been studied. The metal-to-metal distance reaches 24 Å for the longest (n = 3) spacer in the series. For all of the dyads in a room-temperature CH3CN solution, quenching of the typical metal-to-ligand charge-transfer luminescence of the Ru-based chromophoric unit is observed, indicating that an efficient intramolecular photoinduced electron transfer from the excited Ru moiety to the Rh-based unit takes place. The rate constants for the electron-transfer process have been determined by time-resolved emission and absorption spectroscopy in the nanosecond and picosecond time scale. An exponential dependence of experimental transfer rates on the bridge length is observed, consistent with a superexchange mechanism. An attenuation factor of 0.65 Å-1 is determined, in line with the behavior of other systems containing oligo-p-phenylene spacers. Interestingly, for n = 3, the presence/absence of hexyl substituents in the central p-phenylene ring causes a 10-fold difference in the rates between otherwise identical dyads. This comparison highlights the importance of the twist angle between adjacent spacers on the overall through-bond donor-acceptor coupling. (literal)
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