Date of Graduation

Spring 2008

Degree

Master of Science in Chemistry

Department

Chemistry

Committee Chair

Mark Richter

Keywords

electrogenerated chemiluminescence, electrochemistry, photoluminescence, hydroxyquinoline, porphyrin, fluorinated solvents

Subject Categories

Chemistry

Abstract

The photoluminescence, electrochemistry, and electrogenerated chemiluminescence (ECL) of two previously unstudied organometallic systems have been investigated. ECL involves the generation of light from chemicals in solution using electricity. The lithium salts of 8-hydroxyquinoline and 2-methyl-8-hydroxyquinoline and a porphyrin coordinated polypyridyl ruthenium (II) complex were studied for their potential applications as ECL luminophores. In addition, the effects of aromatic and hydroxylic fluorinated solvents on ECL systems were also investigated. The lithium salts of hydroxyquinoline complexes were shown to emit ECL in the blue-green region of the spectrum making them valuable additions to the luminophore library. The complex formed from meso-tris-3,4-dimethoxyphenyl-mono-(4-pyridyl)porphyrin (H2Mpy3,4DMPP) coordinated to [Ru(bpy)2Cl]+ produced red ECL emission at 656 nm. ECL generated via annihilation of organic luminophores such as 9,10-diphenylanthracene was shown to be affected by the polarity and radical anion stabilization capabilities of aromatic fluorinated solvents. Matrix effects of the well-studied system involving tris-2,2'-bipyridyl) ruthenium (II) and tri-n-propylamine were investigated by the addition of hydroxylic solvents. Fluorinated and non-fluorinated alcohols and water:alcohol solvent systems showed in some cases dramatic increases in ECL emission (6 – 270 fold). The increase in ECL emission by use of hydroxylic solvents may prove useful in diagnostic or environmental applications where greater sensitivity and detection limits are required.

Copyright

© David J. Vinyard

Campus Only

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