Charge-transfer absorption and emission resulting from long-range through-bond interaction; exploring the relation between electronic coupling andelectron-transfer in bridged donor-acceptor systems.

Abstract

The electronic absorption- and emission spectra of seven (D)onor-(A)cceptor systems are studied with the general structure D-bridge-A, where the bridge consists of an extended, rigid, saturated hydrocarbon skeleton that separates D and A by distances ranging from 3 to 12 CC σ-bonds. Across bridges with a length up to six σ-bonds sufficient electronic interaction occurs to cause a detectable perturbation of the electronic absorption spectra and for lower homologues this leads to the appearance of discrete intramolecular charge-transfer absorptions with an intensity that is strongly enhanced by intensity borrowing from symmetry-matched local transitions. In the fluorescence spectra discrete charge-transfer (CT) type emission has been detected for bridge lengths up to ten σ-bonds. The radiative transition probability of this CT emission provides a direct measure for the electronic coupling matrix element (H da) between the charge-separated- and the groundstate. The magnitude of H da is found to decrease exponentially with the number of intervening σ-bonds from 850 cm −1 at 3-bond separation to 17.6 cm −1 at 10-bond separation. Furthermore the rate of charge-recombination in the compounds studied is found to be proportional to the square of H da, thus providing an experimental verification of this often implied “golden rule” relation.