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Abbreviations: TPP=5,10,15,20-tetraphenylporphyrin; 4′MPyP= 5-(4′-pyridyl)-10,15,20-triphenylporphyrin; 4′TPyP=5,10,15,20-tetra-(4′-pyridyl)porphyrin; 3′MPyP=5-(3′-pyridyl)-10,15,20-triphenylporphyrin; 3′TPyP=5,10,15,20-tetra(3′-pyridyl)porphyrin.
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We thank a referee for pointing out this problem in an early version of this paper.
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The fluorescent emission in quenched by about 5% in going from degassed to aerated solution. This small effect does not arise from diffusional quenching of the singlet state by oxygen (it is roughly the same for Fb and Zn, despite the strong difference in singlet lifetime and is not accompanied by a parallel lifetime quenching). It most likely corresponds to the quenching of a small amount of delayed fluorescence, ref. [36], arising from repopulation of the singlet after intersystem crossing to the (oxygen sensitive) triplet.
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-1 for all the monomeric models studied.
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In a covalently linked donor-acceptor system, both covalent and electrostatic factors may alter the energy of the charge transfer state with respect to the simple algebraic sum of the redox potentials of the units. Given the weakly coupled nature of these supramolecular systems, covalent corrections are likely to be negligible in this case. The electrostatic work term can be accounted for by the use of standard expressions, ref. [43].
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Collin, J.-P.4
Sauvage, J.-P.5
Sour, A.6
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79
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0001518798
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J.-P. Sauvage, J.-P. Collin, J-C. Chambron, S. Guillerez, C. Coudret, V. Balzani, F. Barigelletti, L. De Cola, L. Flamigni, Chem. Rev., 1994, 94, 993.
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Sauvage, J.-P.1
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Chambron, J.-C.3
Guillerez, S.4
Coudret, C.5
Balzani, V.6
Barigelletti, F.7
De Cola, L.8
Flamigni, L.9
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80
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0346374289
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note
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This is a true symmetry axis only for the perpendicular arrays. It could also be considered for the canted arrays to describe the local symmetry of the axial junction.
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81
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33847089265
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D. Spangler, G. M. Maggiora, L. L. Shipman, R. E. Chirtoffersen, J. Am. Chem. Soc. 1977, 99, 7478.
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J. Am. Chem. Soc.
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Spangler, D.1
Maggiora, G.M.2
Shipman, L.L.3
Chirtoffersen, R.E.4
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82
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85088082818
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note
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[55]
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-
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83
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0002312013
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Ed.: D. Dolphin, Academic Press, New York, Chapter 1
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M. Gouterman in The Porphyrins, vol. 3 (Ed.: D. Dolphin), Academic Press, New York, 1978, Chapter 1.
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(1978)
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Gouterman, M.1
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84
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0347003495
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note
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[56, 57] cyclic systems with π-π* excited states cannot generally meet the overlap conditions required for undergoing Dexter energy transfer from an axial π-π* chromophore.
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86
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1842851147
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R. Cave, P. Siders, R. A. Marcus, J. Phys. Chem. 1986, 90, 1436.
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J. Phys. Chem.
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Cave, R.1
Siders, P.2
Marcus, R.A.3
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87
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0345743174
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note
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[59]
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-
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88
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0002115139
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H. Levanon, A. Regev, P. K. Das, J. Phys. Chem. 1987, 91, 14.
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(1987)
J. Phys. Chem.
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Levanon, H.1
Regev, A.2
Das, P.K.3
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89
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0346374285
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note
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In the perpendicular and canted arrays, respectively, the center-to-center distances are about 9.8 and 8.6 Å, and the number of bonds intervening between the porphyrin rings is six and five.
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-
-
-
90
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0347004138
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note
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-1, respectively. In these systems, the center-to-center distance was about 13.6 Å and the through-bond pathway between the porphyrin rings involved 15 bonds.
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-
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91
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0001096017
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A. Brun, A. Harriman, V. Heitz, J-P. Sauvage, J. Am. Chem. Soc. 1991, 113, 8657.
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J. Am. Chem. Soc.
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Brun, A.1
Harriman, A.2
Heitz, V.3
Sauvage, J.-P.4
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92
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0347004139
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note
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The phenyl rings on TPP are hindered with respect to rotation about the C(meso)-C(phenyl) bond and are nearly perpendicular to the Ru(TPP) mean plane. Therefore the ortho and meta protons on one side of each phenyl ring (endo-H) fall into the anisotropic region of the perpendicular pyridylporphyrin and experience its shielding effect; their resonances are consequently shifted upfield compared to those of the corresponding exo protons.
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