Synthetic and geometric perturbations of the excited states of metal-polypyridine systems
Abstract
This work encompasses three chapters investigating modifications to the excited states of ruthenium(II) and copper(I) polypyridine systems. The main emphasis is on understanding what changes occur when the polypyridine ligands surrounding the metal center are modified. The synthetic modifications are those done in order to create new ligands with specialized steric and electronic characteristics. The geometric modifications refer to environmental changes placed on the coordination complex. The photophysical properties that are a result of the changes are studied, characterized, and discussed in order to better understand the governing factors of the excited states. Chapter I focuses on electronic modifications of ruthenium(II) bis-terpyridine. The new compounds are then employed as luminescent molecular temperature sensors. The research was done in conjunction with Dr. John Sullivan of the Aerospace Engineering Department at Purdue University and the sensors were evaluated in a cryogenic wind tunnel at the National Aerospace Laboratory in Japan. This project has lead to the development of luminescent sensors that are effective at sensing shock waves at cryogenic temperatures. This is the first time a shock wave has been visualized at cryogenic temperatures. This method of detection is an improvement over existing methods as it is cheaper, easier, and gives a complete map of the wind tunnel model. The second and third chapters deal with copper(I) bis-phenanthroline complexes. In chapter 2, synthetic modifications to some phenanthroline ligands lead to new complexes that resist quenching by Lewis bases. The third chapter studies the photophysics of the copper complexes in the solid state. In this chapter, the solid state geometry, dictated by the crystal structure, is shown to have a dramatic effect on the photochemistry of the copper compounds. Also in this chapter is the first reported emission from a copper phenanthroline, with no substituent in the 2,9 positions.
Degree
Ph.D.
Advisors
McMillin, Purdue University.
Subject Area
Chemistry
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