Photoprocesses in Metal Containing Molecules

Author: Wrighton, Mark Stephen

Year: 1972

Degree: Dissertation (Ph.D.)

Advisor: Hammond, George Simms

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/vty0-hp05

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document.

Recent results obtained in the area of transition metal photochemistry are presented. Previous developments in this field are included. The two introductory chapters deal with structure, bonding, and electronic absorption spectroscopy of transition metal complexes. The remaining six chapters deal with pathways for decay of electronically excited states: radiative decay, nonradiative decay, electronic energy transfer, redox photochemistry, photosubstitution, and photoreactions of the coordinated ligands.

Highlights of this work include new convincing evidence for assigning the low lying transitions in [...] metal carbonyls as ligand field excitations; the first definitive study of luminescence phenomena of metal carbonyls; a study of the nonradiative decay of metal carbonyl excited states with the conclusion that specific ligands can dominate the process of nonradiative decay; the first correlation of the quenching activity of a transition metal complex and its electronic properties; intramolecular energy transfer studies where one chromophore is a transition metal complex; data showing that the direct formation of CO(II) occurs via photolysis of some disubstituted cyanocobaltate(III) complexes; presentation of an associative type mechanism for the photoaquation of [...]; a description of a set of considerations (Wrighton-Gray rules) to predict and interpret photo substitution reactions; and a discussion of the photoreactivity of alkenes, dienes, and stilbenes when coordinated to Cr(0), Mo(0) or W(0).

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