Chemistry and Chemical Biology ETDs

Publication Date

1-18-1871

Abstract

A theoretical and experimental investigation of a number of transition-metal complexes was conducted. The compounds of primary interest were six-coordinated complexes containing group VIII metal ions belonging to the second and third transition series. The investigation involved the synthesis and purification of the compounds, the measurement of absorption and emission spectra and luminescent lifetimes, and the analysis of the observed spectral properties using a crystal-field model based on solutions of large secular determinants.

The effects of variations of the Racah parameters on the energy­level diagrams of dn ions {n = 2,3, ... ,8) in an octahedral crystal field were evaluated. The effect of spin-orbit interaction in octa­hedral complexes was incorporated into the model for complexes involving diamagnetic ions with a d6 configuration. Energy-level diagrams were calculated and plotted for specific compounds of Rh{III) and Ir(III) with D4 symmetry. The calculated energy levels obtained for these systems allowed the interpretation of the observed spectral properties of the complexes within the framework of the model. Additional properties of the complexes were predicted on the basis of the model.

Complexes of both d5 and d6 configuration ions were examined. The d5 systems failed to luminesce. The d6 systems displayed, as a general rule, a measurable luminescence. Criteria were proposed for the presence or absence of luminescence from transition-metal complexes.

Language

English

Document Type

Dissertation

Degree Name

Chemistry

Level of Degree

Doctoral

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Illegible

Second Committee Member

Roy Dudley Caton Jr.

Third Committee Member

Nicholas Ernest Vanderborgh

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