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Lookup NU author(s): Dr Ben Allen, Professor Andrew Benniston, Emeritus Professor Anthony Harriman, Irantzu Llarena, Craig Sams
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A small series of p-quaterphenyl derivatives has been prepared in which the dihedral angle (φ) for the two central rings is constrained by dialkoxy spacers of varying length. The photophysical properties of these compounds remain comparable, but there is a clear correlation between the rate constants for nonradiative decay of both singlet and triplet excited states and φ in fluid solution. The rates tend toward a minimum as φ approaches 90°. These effects are attributed to the general phenomenon of extended delocalization and can be traced to a combination of changes in the Huang-Rhys factor and the electron-vibrational coupling matrix element, both relating to displacement of the relevant potential energy surfaces and to the medium-frequency vibronic mode coupled to decay. The latter effect arises because of different levels of conjugation in the ground-state molecule. Such findings might have important implications for the design of improved light-emitting diodes. A similar angle dependence is noted for the yield of the π-radical cation formed on photoionization in a polar solvent, but here, the effect is due to variations in the respective energy gaps between the relevant excited states. © 2007 American Chemical Society.
Author(s): Allen BD, Benniston AC, Harriman A, Llarena I, Sams CA
Publication type: Article
Publication status: Published
Journal: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Year: 2007
Volume: 111
Issue: 14
Pages: 2641-2649
ISSN (print): 1089-5639
ISSN (electronic): 1520-5215
Publisher: American Chemical Society
URL: http://dx.doi.org/10.1021/jp0669660
DOI: 10.1021/jp0669660
PubMed id: 17388362
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