Chemistry and Chemical Biology ETDs

Publication Date

6-2-1964

Abstract

The tris(2,2'-bipyridine)- and tris(l,10-phenanthroline) complexes of iron(II), ruthenium(II), and osmium(II) were synthesized, purified, and characterized by analyses. The solution absorption spectra of the compounds were measured both in the ultraviolet and visible regions. The observed ultraviolet absorption bands of the ruthenium and osmium complexes were assigned entirely to transitions, the prominent bands being assigned to ligand (perturbed) transitions by comparison with the published assignments of the corresponding bands in analogous iron complexes. The visible absorption spectra for iron(II) and ruthenium(II) complexes were attributed entirely to singlet-singlet charge transfer transitions. The strong visible absorption bands of osmium(II) complexes were also assigned to singlet-singlet charge transfer transitions. The origin of the weak and low energy visible transitions in these compounds was discussed. Luminescence spectra of both ruthenium complexes were measured and the origin of the transition giving rise to the emission spectra was discussed. The lifetimes of the luminescences observed for both ruthenium compounds were measured. Luminescence from osmium complexes was also observed. The origin of this luminescence was considered. A tentative assignment of the transition responsible for the luminescence observed from ruthenium and osmium in both 2,2'-bipyridine and 1,10-phenanthroline complexes was forwarded. The available experimental information for the complexes was collected and displayed on energy level diagrams. The radically different behavior of the iron complexes under excitation compared to the ruthenium and osmium complexes was discussed briefly in terms of a simplified crystal field model for the compounds.

Project Sponsors

I wish sincerely to thank Dr. G. A. Crosby for his invaluable aid and support throughout this work. The research presented in this thesis was sponsored by the United States Air Force and the National Science Foundation.

Language

English

Document Type

Thesis

Degree Name

Chemistry

Level of Degree

Masters

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Glenn Arthur Crosby

Second Committee Member

Jesse LeRoy Riebsomer

Third Committee Member

Masanobu Yamauchi

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