By Jochen Mattay, R.F. Khairutdinov, H.D. Roth, P. Suppan, K.I. Zamaraev
1. ok. Zamaraev, R. Khairutdinov: Photoinduced Electron Tunneling Reactions in Chemistry and Biology 2. P. Suppan: The Marcus Inverted area three. H.D. Roth: constitution and Reactivity of natural Radical Cations
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Extra resources for Photoinduced Electron Transfer IV
F. 5 and 11 ,~ for TPP-L-BQ, T P P - L - N Q and TPP-L-AQ, respectively. The efficiency of luminescence quenching (see Table 4) was found to correlate with the change in the free energy, - AG °, of the electron transfer reaction estimated according to the formula (see Sect. 2) - a G ° = E(S,) - E(P/P +) + E ( Q / Q - ) ~40) where E(S1) is the excitation energy of the donor singlet state S 1, E(P/P +) is the porphyrin oxidation potential, and E ( Q / Q - ) is the quinone reduction potential. For the sake of simplicity, the Coulomb term is omitted from the equation since it is the same for all three compounds.
A strong quenching of the fluorescence of the porphyrin fragment by the quinone fragment was discovered in these compounds. The suggestion that the quenching of the porphyrin fragment fluorescence by quinone is due to intramolecular electron transfer was first made in Refs.  and . The Soret band of P-L-Q was found  to be notably broader than that of the free porphyrin, P, and the quantum yield of P fluorescence was observed to decrease by a factor of more than 10 s. Both these facts were explained by electron transfer from the *P fragment to the Q fragment.
The Soret band of P-L-Q was found  to be notably broader than that of the free porphyrin, P, and the quantum yield of P fluorescence was observed to decrease by a factor of more than 10 s. Both these facts were explained by electron transfer from the *P fragment to the Q fragment. The hypothesis about electron transfer from *P to Q has since been repeatedly used to account for the nonexponential character of P fluorescence decay as well as for the dependence of the efficiency of fluorescence quenching on the length of the bridge L, the nature of the porphyrin fragment and the nature of the solvent [124-126].