A Kinetic and Thermodynamic Study of Exciplex Fluorescence Quenching by Ion Pairs
Hartley, Rolfe John
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https://hdl.handle.net/2142/70325
Description
Title
A Kinetic and Thermodynamic Study of Exciplex Fluorescence Quenching by Ion Pairs
Author(s)
Hartley, Rolfe John
Issue Date
1986
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Analytical
Abstract
Tetraalkylammonium salts are shown to quench the fluorescence of the pyrene-N,N-dimethylaniline exciplex in solvents of low dielectric constant. Linear Stern-Volmer plots are obtained for quenching of both lifetime and intensity in dioxane. However, mechanistic complications are implied by intercepts exceeding unity and by the unequal slopes of these plots. Qualitatively similar behavior is observed when the solvents and electrolytes are varied. Historic conductivity data indicate that the quenching species Q in dioxane are aggregates of electrolyte ions, probably ion pairs or quadrapoles. A proposed kinetic model is both qualitatively consistent with the experimental observations and quantitatively self-consistent. An emitting complex formed at a diffusion-controlled rate by an encounter between Q and an exciplex is postulated. The emitting complex is apparently quenched by subsequent encounters with additional Q at rates considerably below the encounter-limited value.
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