Abstract
Electronic absorption spectra of a series of dinaphthyl molecules, in which the naphthyl moieties are separated by a rigid polynorbornyl bridge, together with a corresponding model compound have been measured in n-hexane and acetonitrile solvents. Resonance (molecular exciton) splittings of the naphthalene 1Ag → 21B3u electronic transition are observed and found to be substantially greater than predicted by the usual dipole-dipole model. For the two-bond bridged compound a description of the exciton interaction requires consideration of direct through-space orbital overlap between naphthalenes. Through-space interchromophore orbital overlaps in the four-bond and the six-bond bridged compounds are negligible, and it is concluded that for these systems a significant contribution by a through-bond interaction (involving the σ- and σ*-orbitals of the bridge) leads to the efficient delocalization of the excitation observed. This is the first evidence that exciton interactions can be enhanced by a through-bond interaction.
Original language | English (US) |
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Pages (from-to) | 4345-4349 |
Number of pages | 5 |
Journal | Journal of the American Chemical Society |
Volume | 115 |
Issue number | 10 |
DOIs | |
State | Published - May 1 1993 |
Externally published | Yes |
All Science Journal Classification (ASJC) codes
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry