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Abbreviations used in this paper: bpy = 2,2′-bipyridine; dmb = 4,4′-dimethyl-2,2′-bipyridine; deb = 4,4′-dicarboxy-2,2′-bipyridine; dmp = 4,7-dimethyl-1,10-phenanthroline; BL = 1,2-bis[4-(4′-methyl-2,2′-bipyridyl)]ethane.
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2(dmb) excited states have already disappeared within the laser pulse. Thus, what is monitored in Figure 5A is just the long tail portion of a strongly quenched emission.
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0 -logI(t), is not expected to parallel exactly that of a true emission signal, I(t), except for the "optically diluted" limit (i.e., apparent bleachings with ΔA ≤ 0.1).
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2 = 6.8 μs (84%).
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Sutin, N.5
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83
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0343147773
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note
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The solvent can affect excited-state decay kinetics in several ways. Peculiar to deb-based systems is the possibility that the solvent affects the degree of protonation of the carboxylic groups. In the case of the mononuclear model, this is expected to affect the MLCT excited-state energy, and thus the energy gap for radiationless deactivation. In the dyads, this is expected to affect Rh(III)/(II) redox potential, and thus the driving force of the intramolecular electron transfer step. In aqueous media, where the protonation of the carboxylic groups can be precisely controlled, a gradual acceleration in decay rate with increasing degree of protonation has been demonstrated for the dyads (M. T. Indelli, unpublished results).
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84
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0342713238
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note
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While the carboxylate groups grafted to the surface are certainly deprotonated, the actual number of groups grafted and the overall state of protonation are not known. The arrangement of Figure 10 has simply been chosen for graphical purposes.
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-
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86
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33748394800
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(b) Tachibana, Y.; Moser, J. E.; Grätzel, M.; Klug, D. R.; Durrant, J. R. J. Phys. Chem. 1996, 100, 20056.
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(1996)
J. Phys. Chem.
, vol.100
, pp. 20056
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Tachibana, Y.1
Moser, J.E.2
Grätzel, M.3
Klug, D.R.4
Durrant, J.R.5
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87
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0343147774
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(c) Rehm, J. M.; McLendon, G. L.; Nagasawa, Y.; Yoshihara, K.; Moser, J.; Grätzel, M. J. Phys. Chem. 1966, 100, 9777.
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(1966)
J. Phys. Chem.
, vol.100
, pp. 9777
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-
Rehm, J.M.1
McLendon, G.L.2
Nagasawa, Y.3
Yoshihara, K.4
Moser, J.5
Grätzel, M.6
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88
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0001893021
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Argazzi, R.; Bignozzi, C. A.; Heimer, T. A.; Meyer, G. J. Inorg. Chem. 1996, 36, 2.
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(1996)
Inorg. Chem.
, vol.36
, pp. 2
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Argazzi, R.1
Bignozzi, C.A.2
Heimer, T.A.3
Meyer, G.J.4
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89
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0343147775
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note
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70
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-
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90
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0342713236
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note
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This model assumes that no recombination between injected electrons and Ru(III) centers takes place during this period. Considering this assumption, the F value estimated from the transient spectral changes should be taken as a lower limit for the efficiency of stepwise injection.
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-
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91
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0002243915
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2 (eqs 4 and 5) and of intramolecular back electron transfer (eq 6) were set to be much faster then the instrument response for the measured data. Note that on the 100 ns time scale these data was simulated over, interfacial charge recombination (eq 9) does not alter the simulated spectra, consistent with experimental observations of Figure 9.
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(1993)
J. Photochem. Photobiol. A: Chem.
, vol.70
, pp. 29
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Yoshimura, A.1
Hoffman, M.Z.2
Sun, H.3
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92
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0342278195
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note
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2, under our experimental conditions, of -0.50 V vs SCE.
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93
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0342278194
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Manuscript in preparation
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Kleverlaan, C. J, et al. Manuscript in preparation.
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Kleverlaan, C.J.1
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