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Intramolecular energy transfer in the covalently linked dimeric complex ((bpy)/sub 2/Ru(b-b)Ru(biq)/sub 2/)/sup 4 +/

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100333a008· OSTI ID:6333673

The covalently linked dimer ((bpy)/sub 2/Ru(b-b)Ru(biq)/sub 2/)/sup 4 +/ (bpy = bipyridine, b-b = 1,4-bis(2-(4'methyl-2,2'-bipyridyl-4-yl)ethyl)benzene, and biq = 2,2'-biquinoline) was prepared, and its photophysical behavior in room-temperature solutions and low-temperature glasses was examined. Luminescence is observed from both Ru ..-->.. bpy metal-to-ligand charge-transfer (MLCT) and Ru ..-->.. biq MLCT states; however, the Ru ..-->.. bpy emission is nearly completely quenched in acetonitrile solutions. In low-temperature (13 K) ethanol/methanol glasses a rise and fall is observed in the Ru ..-->.. biq luminescence decay, clearly indicating sensitization by the Ru ..-->.. bpy MLCT emission. The temperature dependence of the Ru ..-->.. bpy MLCT emission of the dimer and the emission of ((bpy)/sub 2/Ru(b-b))/sup 2 +/ can be fit to a model in which emission occurs from each of two MLCT states separated by 65-80 cm/sup 1/. The decay of the ((bpy)/sub 2/Ru(b-b)) center of the dimer is dominated by energy transfer to the Ru ..-->.. biq MLCT manifold. The relative energy-transfer rates from each of two Ru ..-->.. bpy MLCT states of the ((bpy)/sub 2/Ru(b-b)) center of the dimer are discussed in terms of a dipolar coupling mechanism.

Research Organization:
Tulane Univ., New Orleans, LA (USA)
OSTI ID:
6333673
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:22; ISSN JPCHA
Country of Publication:
United States
Language:
English