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Description
Title: | Multi-Method Investigation of the Mechanism of Surfactant-Induced Chromatotropism of Metal-Chelometric Dye Complexes |
Author(s): | Ogawa, Mark Kenneth |
Department / Program: | Chemistry |
Discipline: | Chemistry |
Degree Granting Institution: | University of Illinois at Urbana-Champaign |
Degree: | Ph.D. |
Genre: | Dissertation |
Subject(s): | Chemistry, Analytical |
Abstract: | The mechanism by which certain surfactants change the ultraviolet-visible (UV-vis) spectroscopic properties of certain metal-dye complexes has been largely ignored in the chemical literature. In this manuscript a model is developed to describe this mechanism. Intramolecular forces among surfactant molecules and host molecules are described to emphasize the importance of specific interactions to the mechanism. A review of the theoretical basis of UV-vis spectroscopic changes in dyes (chromatotropism) is given followed by application to the dyes of interest in this study. UV-vis spectra of the dyes, metal-dye complexes, and metal-dye-surfactant systems are analysed and a relationship between the symmetry of the chromophore and the UV-vis spectroscopic properties is described. This is the basis of the mechanistic model which postulates that the metal ion of the complex migrates from an asymmetric binding site to a symmetric binding site of the dye upon interaction with surfactant. Evidence in support of the molecular structures of the metal-dye complexes and metal-dye-surfactant systems proposed by the model is given in the analysis of infrared (IR) and Raman (R) spectra of these species. Structures of two metal-dye surfactant systems are proposed on the basis of the vibrational data. Thermodynamics of the rearrangements proposed by the model are investigated using ab-initio Hartree-Fock molecular orbital calculations. |
Issue Date: | 1987 |
Type: | Text |
Language: | English |
Description: | 335 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987. |
URI: | http://hdl.handle.net/2142/77257 |
Other Identifier(s): | (UMI)AAI8803159 |
Date Available in IDEALS: | 2015-05-13 |
Date Deposited: | 1987 |
This item appears in the following Collection(s)
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Dissertations and Theses - Chemistry
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Graduate Dissertations and Theses at Illinois
Graduate Theses and Dissertations at Illinois