Application of d6 Transition Metal Complexes as Luminescence-Based Sensors

Leavens, Bethany Bree Hueholt, Department of Chemistry, University of Virginia
Demas, James, Department of Chemistry, University of Virginia
Bryant, Robert, Department of Chemistry, University of Virginia
Venton, Jill, Department of Chemistry, University of Virginia

Luminescence-based analyte sensing techniques have found widespread use due to their sensitivity, relatively low cost, and ease of implementation. One common approach employed in the design of luminescent probes is a "host-guest" strategy wherein a target analyte affects the photophysical properties of the sensor in a measurable way; thus allowing for quantification of the analyte. Described herein are the preparation of luminescent complexes of rhenium(I), iridium(III), osmium(II), and ruthenium(II) according to this strategy and their application towards the detection of several analytes. The photophysical properties of these complexes are studied via emission and lifetime measurements. A lead(II) quantification method based upon the formation and extraction of luminescent Pb 4 Br 3- 11 clusters is described. This technique allows for measurement of the heavy metal in aqueous solutions. The limit of detection for this method is 34 nM. In addition, this work includes the design and synthesis of ruthenium(II) and rhenium(I) complexes intended for use as transition metal complex ionic liquids. Observation of the lifetime as a function of temperature reveals divergent behavior in comparison with analogous complexes.

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PHD (Doctor of Philosophy)
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