Effect of coordinated ligands on interporphyrin photoinduced-electron-transfer rates

D. Gust, Thomas Moore, Ana Moore, H. K. Kang, J. M. DeGraziano, P. A. Liddell, G. R. Seely

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Abstract

The effect of coordination of various pyridines on the rate of photoinduced interporphyrin electron transfer in a molecular dyad consisting of a zinc porphyrin covalently linked to a free base porphyrin moiety has been investigated using time-resolved fluorescence techniques. Coordination of pyridine itself to the zinc ion results in a nearly 30-fold increase in the rate constant for one of the photoinduced-electron-transfer reactions. In similar studies with a series of pyridine ligands bearing substituents with electron-donating or accepting properties, the data correlate well with the substituent constant under the Hammett linear free energy relationship. The reaction constant ρ has a value of -0.35, which indicates that the rate of electron transfer is increased by electron donation to the zinc porphyrin. Electrochemical experiments with a poorly-coordinating electrolyte suggest that this donation stabilizes the interporphyrin charge-separated state, in which the zinc porphyrin moiety is positively charged, and that this stabilization in turn leads to a larger rate constant for electron transfer. Effects of this type undoubtedly play a role in metalloproteins in which a porphyrin metal ion is ligated to the protein. They may also affect the interpretation of solvent effects noted in electron-transfer reactions involving metallated porphyrins.

Original languageEnglish (US)
Pages (from-to)13637-13642
Number of pages6
JournalJournal of physical chemistry
Volume97
Issue number51
DOIs
StatePublished - Jan 1 1993

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ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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