Journal
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
Volume 170, Issue 3, Pages 287-297Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jphotochem.2004.08.018
Keywords
tetraphenylporphyrinatoantimony(V) complex; boron-dipyrrin chromophore; axial ligands; intramolecular energy transfer
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Tetraphenylporphyrinatoantimony(V) complexes, linked to boron-dipyrrin chromophores on axial ligands, were synthesized. The fluorescence spectra of 1a, 1b and 1c (3-[4-(N,N'-difluorobomyl-5-dipyrrinyl)phenyl]propoxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1a); 6-[4-(N,N'-difluorobomyl-5-dipyriinyl)phenyl]hexyloxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1b); bis {3-[4(N,N'-difluorobornyl-5-dipyrrinyl)phenyl]propoxo}antimony(V) tetraphenylporphyrin bromide (1c)) were analyzed under the excitations of N,N'-difluorobornyl-5-dipyrrinylphenyl (Bdpy) and tetraphenylporphyrinatoantimony(V) (Sb(TPP)) chromophores. Under the irradiation of Bdpy chromophore, the excitation energy was transferred from Bdpy chromophore to the Sb(TPP) moiety at 0.13-0.40 of the quantum yields, even in a polar solvent. On the other hand, the emission of Sb(TPP) chromophores was quenched by Bdpy chromophores at rate constants of 10(8)-10(9) s(-1), independent of on the solvent polarity. Under the excitation of the Bdpy chromophore of 1d (3-[4-(N,N'-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(phenyloxo)antimony(V) tetraphenylporphyrin bromide) involving both the Bdpy and the phenoxy chromophores on the axial ligands, the excited singlet state of the Sb(TPP) chromophore generated by the energy transfer from the Bdpy chromophore was quenched by the phenoxy ligand via non-radiative processes involving electron transfer. However, rapid back electron-transfer may occur because no absorption of the anion radical of Sb(TPP) was observed by nanosecond laser photolysis. (c) 2004 Published by Elsevier B.V.
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