Effect of High Pressure on the Luminescence of Indoles and Metalloporphyrins
Politis, Theodore George
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https://hdl.handle.net/2142/69724
Description
Title
Effect of High Pressure on the Luminescence of Indoles and Metalloporphyrins
Author(s)
Politis, Theodore George
Issue Date
1981
Department of Study
Chemical Engineering
Discipline
Chemical Engineering
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Engineering, Chemical
Abstract
The effects of pressure on the luminescence properties of indoles and metalloporphyrins were investigated. The indole and indole derivatives were studied in liquid solvents up to 10 kilobars. The metalloporphyrins were studied in both fluid and plastic solvents. Radiative and non-radiative rates have been calculated from the experimental data.
The indole and its derivatives exhibit only fluorescence. The change of non-radiative rates with pressure in all solvents except water and methanol are determined by viscosity effect. The radiative rates and peak shifts are controlled by the dielectric constant of the solvent. Some peculiarities have been observed when water and methanol were used as solvents.
Two different groups of metalloporphyrins have been studied. The first group includes the free base-Tetraphenyloporphyrin and metallocomplexes with a closed shell metal at the center (Zn, Mg). The second group includes complexes with an open shell metal at the center (Cu, Cr). The radiative rates have been found always to change proportionally to the square of refractive index. The non-radiative rates are either controlled by viscosity or by the relative position of the energy levels.
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