Electronic mediated “through-bond

A single-crystal X-ray diffraction study revealed that the two ferrocene units are in anti conformation. Cyclic voltammetric results are in accord with a strong interaction between the iron centres. Electronic interactions through bonds are mediated by the bridging dimethylsilyl groups and this is discussed in more detail in Section n.E.3. 

Keywords Electron Tansfer m Energy Transfer m Through-Bond Coupling m Superexchange m Molecular Wires m Solvent-Mediated Electron Transfer m Electron Transfer in DNA m Charge Separation m Electron Transfer Through H-Bonds... 

Electron Transfer /Mediated Through Hydrogen Bonds... 

Through-Bond-Mediated Electronic Excitation Energy Transfer... 

N. Lokan, M. N. Paddon-Row, T. A. Smith, M La Rosa, K P. Ghiggino, S. Speiser, Highly Efficient Through-Bond-Mediated Electronic Excitation Eneigy Transfer Taking Place Over 12 A , J. Am Chem Soc 1999,121,2917-2918. 

K. D. Jordan and M. N. Paddon-Row, Analysis of the interactions responsible for long-range through-bond-mediated electronic coupling between remote chromophores attached to rigid polynorbornyl bridges, Chem. Rev., 92 (1992) 395-410. 

Upon photoexcitation fast intramolecular charge-separation is observed similar in rate and in temperature dependence to the early steps of photosynthesis. It is proposed that the bridges play an active role in mediating electron transfer via through-bond interaction, thereby enhancing the rate of charge separation significantly as compared to other model systems. 

Although no evidence has been found that the monomeric bacteriochlorophyll unit, which is intercalated between the special pair and the pheophytin (see Fig. 1), actually acquires an electron, it should be noted that also this unit may act as a mediator via a super-exchange mechanism (Kuznetsov and Ulstrup, 1982 Miller and Beitz, 1981), which is conceptually related to through-bond interaction. 

Through-bond electron transfer Intramolecular electron tranffer for which the relevant electronic interaction between the donor and acceptor sites is mediated by through-bond interaction, i.e. via the covalent bonds intercoimecting these sites, as opposed to through-space interaction. 

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