Abstract
The interaction of singlet trans-stilbene with several trialkylamines and diamines in acetonitrile solution has been investigated by a combination of steady-state measurements and time-resolved resonance Raman spectroscopy. Adduct formation between trans-stilbene and acyclic monoamines is proposed to occur via a short-lived exciplex (contact radical ion pair) intermediate, which is not quenched by ground-state amine. A solvent-separated radical ion pair is formed either directly from an encounter complex or via the exciplex and decays by intersystem crossing to yield triplet trans-stilbene, dissociation to yield free radical ions, or quenching by ground-state amine. Intersystem crossing is more rapid for the diamines vs. monoamines, resulting in a lower yield of free radical ions. Quenching of the solvent-separated radical ion pair by ground-state amine is subject to the same stereoelectronic effect as observed for exciplex quenching in nonpolar solvent. Free trans-stilbene anion radical decay is by recombination with amine cation radical and is independent of amine structure or concentration.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 708-715 |
| Number of pages | 8 |
| Journal | Journal of the American Chemical Society |
| Volume | 106 |
| Issue number | 3 |
| DOIs | |
| State | Published - Feb 1 1984 |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry