Electrogenerated chemiluminescence (ECL) studies were performed on several interesting compounds. A series of silole-based (silacyclopentadiene) chromophores was examined to understand the effects of their structure on the electrochemistry and spectroscopy of these compounds. A case was observed in which high steric hindrance improved ECL by inhibiting internal conversion and protecting radicals from secondary reactions. Another case was observed in which steric effects induced a rotation in the silole substituents, increasing secondary reactions and lowering quantum efficiency ([Phi subscript PL]). Spiro-FPA, which consists of two DPA centers, exhibits excimer formation despite high steric hindrance, due to its ability to form di-ions, which have a greater electrostatic attraction to one another than mono-ions. The compound (dppy)BTPA is a highly solvatochromic, boron-containing chromophore that was examined in a variety of solvents. Of note is the emission in pure acetonitrile, which is prominent in the ECL spectrum, but barely visible in the photoluminescence. Finally, B⁸ amide, a compound based on the laser dye, BODIPY, was examined. It exhibited unusual ECL characteristics. These include a strong, long-wavelength emission and transients that are clearly visible for 20 min or more, but display dramatically varying light intensities with each pulse. Evidence for the contribution of a film formed with the oxidation product is presented. Additionally, ECL simulations are performed using a general physics software package to better understand some of the observed phenomena.
Identifer | oai:union.ndltd.org:UTEXAS/oai:repositories.lib.utexas.edu:2152/3667 |
Date | 29 August 2008 |
Creators | Sartin, Matthew McCullough, 1982- |
Contributors | Bard, Allen J. |
Source Sets | University of Texas |
Language | English |
Detected Language | English |
Type | Thesis |
Format | electronic |
Rights | Copyright © is held by the author. Presentation of this material on the Libraries' web site by University Libraries, The University of Texas at Austin was made possible under a limited license grant from the author who has retained all copyrights in the works. |
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