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In principle, the supramolecular nature of the triads can also be checked by electrochemistry. In practice, the cyclic voltammetry of the triads (dichloromethane, glassy carbon working electrode) is a reasonable superposition of those of the model molecules, but substantial peak broadening and poor reversibility (likely caused by electrode absorption) prevents a precise comparison of potential values.
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In principle, the supramolecular nature of the triads can also be checked by electrochemistry. In practice, the cyclic voltammetry of the triads (dichloromethane, glassy carbon working electrode) is a reasonable superposition of those of the model molecules, but substantial peak broadening and poor reversibility (likely caused by electrode absorption) prevents a precise comparison of potential values.
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74
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47049129311
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25
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25
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77
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84918669584
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2, at an estimated center-to-center distance of 14.8 Å, amounts to 0.11 eV.
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2, at an estimated center-to-center distance of 14.8 Å, amounts to 0.11 eV.
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78
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0010104094
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2 = 4, RDA = 14.8 Å). Calculations performed using PhotochemCAD (Du, H.; Fuh, R. A.; Li, J.; Corkan, A; Lindsey, J. S. Photochem. Photobiol. 1998, 68, 141-142).
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2 = 4, RDA = 14.8 Å). Calculations performed using PhotochemCAD (Du, H.; Fuh, R. A.; Li, J.; Corkan, A; Lindsey, J. S. Photochem. Photobiol. 1998, 68, 141-142).
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81
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47049112564
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Femtosecond results obtained with excitation at 550 nm (ca. 60% excitation of the Zn porphyrin chromophore) were practically the same except for small differences in the spectral changes taking place in the first few picoseconds as those reported below for excitation at 590 nm (selective perylene bisimide excitation). The time constant for the conversion of the upper Zn porphyrin chromophores to the lower perylene bisimide by singlet energy transfer, 3.4 ps, can be obtained upon 550 nm excitation by monitoring the decay of the *ZnP(S1) absorption at 440 nm (Figure S2 of supporting material).
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Femtosecond results obtained with excitation at 550 nm (ca. 60% excitation of the Zn porphyrin chromophore) were practically the same except for small differences in the spectral changes taking place in the first few picoseconds as those reported below for excitation at 590 nm (selective perylene bisimide excitation). The time constant for the conversion of the upper Zn porphyrin chromophores to the lower perylene bisimide by singlet energy transfer, 3.4 ps, can be obtained upon 550 nm excitation by monitoring the decay of the *ZnP(S1) absorption at 440 nm (Figure S2 of supporting material).
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82
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0010104094
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With appropriate parameters, n, 1.424; ΦD/T D, 1.4 × 108 s-1; K2, 4, RDA, 15.8 Å, the calculated time constant is ca. 2 ps. Calculations performed using PhotochemCAD Du, H, Fuh, R. A, Li, J, Corkan, A; Lindsey, J. S. Photochem. Photobiol. 1998, 68, 141-142
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2 = 4, RDA = 15.8 Å), the calculated time constant is ca. 2 ps. Calculations performed using PhotochemCAD (Du, H.; Fuh, R. A.; Li, J.; Corkan, A; Lindsey, J. S. Photochem. Photobiol. 1998, 68, 141-142).
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83
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A precise quantitative evaluation of the amount of quenching is prevented by the presence of traces of free, unquenched porphyrin as detected by single-photon-counting techniques
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A precise quantitative evaluation of the amount of quenching is prevented by the presence of traces of free, unquenched porphyrin as detected by single-photon-counting techniques.
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87
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0021133071
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(d) Miller, J. R.; Beitz, J. V.; Huddlestone, R. K. J. Am. Chem. Soc. 1984, 106, 5057-5068.
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Miller, J.R.1
Beitz, J.V.2
Huddlestone, R.K.3
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0345060761
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(e) Newton, M. D. Chem. Rev. 1991, 91, 767-792.
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Newton, M.D.1
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