Ab initio and semiempirical calculations of transfer integrals for electron transfer and energy transfer have been carried out on rigidly linked norbornane-bridged naphthalene dimers to gain insight into the relative importance of through-bond and through-space interactions on photoinduced energy and electron transfer processes. In the absence of direct through-space orbital overlap between the naphthalene moieties, through-bond interaction involving the linking polynorbornane bridge is found to significantly enhance the transfer integrals for electron transfer and triplet-triplet energy transfer. For singlet-singlet energy transfer direct through-space Coulombic interaction between the naphthalene moieties is non-negligible at the separations considered and acts to reinforce the through-bond interaction. The relationship between electron and energy transfer processes and the application of these results to the interpretation of recent experimental data are discussed.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry