Abstract
A series of compounds were designed and synthesized to examine how through-space and through-bond electron delocalization respond to solvent effects. The general strategy involves the study of "dimers" of the distyrylbenzene chromophore held in close proximity by the [2.2]paracyclophane core and a systematic dissection of the chromophore into components with through-space and through-bond electronic delocalization. Steady state and time-resolved fluorescence spectroscopy in a range of solvents reveals a red-shift in emission and an increase in the intrinsic fluorescence lifetime for the emitting state in polar solvents when donor substituents are absent. We propose that through-space delocalization across the [2.2]paracyclophane core is more polarizable in the excited state, relative to the through-bond (distyrylbenzene based) excited state. When strong donors are attached to the distyrylbenzene chromophore, the charge transfer character of the distyrylbenzene-based excited state dominates fluorescence properties.
Original language | English |
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Pages (from-to) | 7435-7443 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 127 |
Issue number | 20 |
DOIs | |
Publication status | Published - 2005 May 25 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry