Through-Space and Through-Bond Effects on Exciton Interactions in Rigidly Linked Dinaphthyl Molecules

Gregory D. Scholes, Kenneth P. Ghiggino, Anna M. Oliver, Michael N. Paddon-Row

Research output: Contribution to journalArticle

127 Scopus citations

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 languageEnglish (US)
Pages (from-to)4345-4349
Number of pages5
JournalJournal of the American Chemical Society
Volume115
Issue number10
DOIs
StatePublished - May 1 1993
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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