Luminescent properties of transition metal compounds

Breeze N Briggs, Purdue University

Abstract

This dissertation focuses on luminescent properties of metal complexes. The first chapter is concerned with the binding interaction of Cu(II) porphyrins with DNA and RNA. The first chapter investigates the interaction of three different porphyrins with a range of DNA and RNA hairpins. The interactions are monitored by absorbance, emission and circular dichroism. The second chapter explores copper-containing [2]pseudorotaxane. The ability for large complexes like rotaxanes to undergo large amplitude motion is of interest. The [2]pseudorotaxanes studies here can mimic elements of functioning molecular machines. The emission, lifetime and quantum yield of four different [2]pseudorotaxanes were measured. The third chapter focused on the synthesis of dipyrromethane-type ligands for porphyrins synthesis. In addition to the synthesis of a range of different starting materials, two different mechanisms were explored as viable methods for synthesis of the H2cD4n. The final chapter focuses on the luminescent properties of quadruply bonded rhenium and technetium compounds. The small overlap of the dxy orbitals on the two metal centers causes a small energy for the 1δ-δ* transition. The energy separation is also large between 1δ-δ* and 3δ-δ*, as a result the emission is derived from the singlet state in these octohalide complexes. The emission, excitation and lifetimes were explored for the first time with the technetium complexes. (Abstract shortened by UMI.)

Degree

Ph.D.

Advisors

McMillin, Purdue University.

Subject Area

Inorganic chemistry

COinS