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68149089273
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The reduction potential of pyrene was estimated from the oxidation potential (1.44 V vs SCE) and the 0-0 band of absorption maximum (340 nm).
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The reduction potential of pyrene was estimated from the oxidation potential (1.44 V vs SCE) and the 0-0 band of absorption maximum (340 nm).
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35
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68149115685
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The CT state energy in solvent x (ECT)X was calculated from the following equation: equation represented where E 1/2, E1/2, e, εx, and εm are half-wave one-electron oxidation and reduction potentials in solvent m, the electronic charge, and the static dielectric constants of solvent x and m, respectively. The r por (6.2 Å) and the rpy (4.0 Å) are the effective ionic radius of porphyrin and pyrene, respectively. These values were obtained by the ab initio MO calculation at the Hartree-Fock 6-31G level. Distance a is the center-to-center distance between the porphyrin and the pyrene moieties (7.7 Å, The following values were used as static dielectric constants: 36.0 (acetonitrile, 25.2 (benzonitrile, 9.10 (dichloromethane, 2.38 (toluene, and 1.88 hexane
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py (4.0 Å) are the effective ionic radius of porphyrin and pyrene, respectively. These values were obtained by the ab initio MO calculation at the Hartree-Fock 6-31G level. Distance "a" is the center-to-center distance between the porphyrin and the pyrene moieties (7.7 Å). The following values were used as static dielectric constants: 36.0 (acetonitrile), 25.2 (benzonitrile), 9.10 (dichloromethane), 2.38 (toluene), and 1.88 (hexane).
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37
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1842415454
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0000857196
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41
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68149105633
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The kf was roughly estimated to be 2.5 x 108 s-1 from the fluorescence quantum yield (Φ0 s2-s2) and the lifetime (to) of S2 state of zinc tetraphenylporphyrin derivatives in acetonitrile by the following equation: equation represented For the calculation, the values for Φ0 s2-s2 of ZnP and τ0 of zinc tetraphenylporphyrin τ0, 3.5 ps)9 were used. The kf was assumed to be the constant in all solvents for the calculation of the kET
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ET.
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