Degree Name

Master of Science (MS)

Semester of Degree Completion

1991

Thesis Director

Mark E. McGuire

Abstract

Based upon the chemiluminescent properties of [Ru(bpy)3]2+ and the proven analytical applications of that complex in the detection of easily reduced anions in solution, a chromatographic detection system was designed utilizing an immobilized form of the Ru(ll) complex. The objective was to create, by electropolymerization, a regenerative chemiluminescent surface on a working electrode. Reductive electropolymerization was accomplished by the use of a [Ru(bpy)3]2+ analog containing the ligand vinylbipyridine. Two analogs, [Ru(vbpy)3][PF6]2 and [Ru(phen)2(vbpy)][PF6]2 were polymerized on platinum, glassy carbon and indium-doped tin oxide working electrodes and evaluated for chemiluminescent emission in an electrochemical cell using oxalate ion. When held at an oxidative potential slightly above the +3/+2 couple of the complex, no chemiluminescence was observed from oxalate at the surface of either polymer. Pulsing the electrode/polymer surface between the potentials known for the +3 and +1 states also did not yield chemiluminescence. A spectral comparison of equivalent solutions of [Ru(vbpy)3][PF6]2 and [Ru(bpy)3][Cl2] indicated significant differences between the spectra of the oxidized form of each solution. The oxidized form of [Ru(vbpy)3][PF6]2 also demonstrated a more rapid reduction to the +2 state in solution than did the oxidized form of [Ru(bpy)3][Cl2]. Significant luminescence intensity differences were also observed between the fluorescence spectra of [Ru(vbpy)3][PF6]2 and [Ru(bpy)3][Cl2]. These properties may prevent the excited state *[Ru(vbpy)3]2+ complex from deactivating via a chemiluminescence pathway. One possible solution to this problem would be to use a monovinyl ruthenium complex such as [Ru(bpy)2(vbpy)][Cl2] with increased [Ru(bpy)3]2+ character.

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