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The use of the value 0.62 nm for the electron transfer distance is made on the basis of consistency with previous studies on related systems. Given the similarity in terms of the coordination environment and solvent condition employed in obtaining the absorption spectra of the mixed valence species, the inherent error in the value of d will be constant for all complexes considered in the present study. It should be noted that the electron transfer distance has been subject to extensive discussion in the literature in particular with respect to delocalization of the donor and acceptor orbitais. See for example: (a) Bublitz, G. U.; Laidlaw, W. M.; Denning, R. G.; Boxer, S. G. J. Am. Chem. Soc. 1998, 120, 6068-6075.
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The use of the value 0.62 nm for the electron transfer distance is made on the basis of consistency with previous studies on related systems. Given the similarity in terms of the coordination environment and solvent condition employed in obtaining the absorption spectra of the mixed valence species, the inherent error in the value of d will be constant for all complexes considered in the present study. It should be noted that the electron transfer distance has been subject to extensive discussion in the literature in particular with respect to delocalization of the donor and acceptor orbitais. See for example: (a) Bublitz, G. U.; Laidlaw, W. M.; Denning, R. G.; Boxer, S. G. J. Am. Chem. Soc. 1998, 120, 6068-6075.
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It should be noted that the use of redox asymmetry, i.e, the difference in redox potential, to assess the degree of internuclear interaction in terms of delocalization is not advisable even in the case of fully symmetric systems, as the electrostatic contribution to asymmetry can be significant. In the present study the inherent asymmetry due to differences in the coordination environment of the metal centers contributes the most to redox asymmetry with delocalization and internuclear interaction making a second order contribution
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It should be noted that the use of redox asymmetry, i.e., the difference in redox potential, to assess the degree of internuclear interaction in terms of delocalization is not advisable even in the case of fully symmetric systems, as the electrostatic contribution to asymmetry can be significant. In the present study the inherent asymmetry due to differences in the coordination environment of the metal centers contributes the most to redox asymmetry with delocalization and internuclear interaction making a second order contribution.
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