Kinetic and Spectroscopic Investigation of The Influence of Conformation and Orbital-Symmetry on Long-Range Intramolecular Donor-Acceptor Interaction

In conformationally well defined systems where an electron-donor (D) and acceptor (A) are interconnected by one ore more arrays of saturated carbon-carbon bonds the D/A interaction is influenced by changes in the length as well as in the configuration of these arrays. This not only affects the kinetics of (photoinduced) electron transfer between D and A, but also the electronic absorption and emission spectra are modified as a result of the presence of a new transition of the charge-transfer type. It is shown that especially charge-transfer emission can yield detailed information about the conformational and orbital-symmetry dependence of D/A interaction, while the effect of these parameters on electron transfer kinetics tends to be masked by concomitant changes in Franck-Condon factors.