title: Rodlike molecules and singlet energy transfer(1)(,)(2)
abstract: In continuing our investigations on rodlike molecules composed of bicyclo[2.2.2]octane units, we studied the effect of interposing a single aromatic ring in the rod. Thus, two [3]-rods were synthesized with the two outer units being bicyclooctyls, the central unit being benzenoid, and with one terminal unit bearing an alpha-naphthyl moiety and the other terminus bearing an acetyl or benzoyl group. Excitation of the alpha-naphthyl group led to fluorescence emission by both the naphthyl and the acetyl units. However, compared to the [1]- and [2]-rods previously studied, transmission of singlet excitation proved to be less efficient as determined by the fluorescence emission and also by the singlet lifetimes obtained from single photon counting measurement. Transmission to the benzoyl group proved more rapid than to the acetyl moiety. In assessing the factors controlling energy transmission, Delta-density determinations were employed to describe the distribution of electronic excitation in such systems. It was observed that despite most of the energy being located in the terminal chromophores, some is distributed in the bicyclooctyl units. The extent of this distribution provides a guide to the facility of through-bond energy transfer. Evidence is presented that energy transfer in the short rods is mainly through-bond while in the longer rods Forster through-space transfer is involved.
authors.affiliation: Chemistry Department of the University of Wisconsin, Madison, Wisconsin, 53706, USA.
authors.initials: HE
authors.lastname: Zimmerman
authors.initials: YA
authors.lastname: Lapin
authors.initials: EE
authors.lastname: Nesterov
authors.initials: GA
authors.lastname: Sereda