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Intramolecular Energy Transfer in Bis-porphyrins Containing Diimine Chelates of Variable Geometry as Spacers

✍ Scribed by Graham Hungerford; Mark Van der Auweraer; Jean-Claude Chambron; Valérie Heitz; Jean-Pierre Sauvage; Jean-Louis Pierre; Dacil Zurita


Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
249 KB
Volume
5
Category
Article
ISSN
0947-6539

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✦ Synopsis


Free-base porphyrin dimers bridged by either 6,6'-diphenyl-2,2'-bipyridine or 2,9-diphenyl-1,10-phenanthroline spacers were synthesized and characterized. Metallation of one of the porphyrins with Zn II allowed us to study intramolecular energy-transfer processes between the Zn II -porphyrin photoreceptor and the freebase porphyrin energy acceptor by time-correlated single-photon counting. The rate of energy transfer was shown to depend strongly on the nature of the bridge, being enhanced by a factor of nearly 6 when comparing the (cis) phenanthroline bridge with the trans-bipyridine bridge. A detailed analysis of the fluorescence decays suggests the presence of two slowly interconverting conformers for the 6,6'-diphenyl-2,2'bipyridine spacer.