The excited states of late transition metal-polypyridine systems in solution and the solid state, and the DNA binding interactions of platinum(II) polypyridyl complexes
Abstract
This work is divided into three chapters and encompasses an understanding of the excited state of various metal-polypyridine complexes. Chapter 1 focuses on the novel Pt(2-(2′-pyridyl)-1,10-phenanthroline)Cl + (Pt(php)Cl+) complex and methyl substituted derivatives. The Pt(php)Cl+ displays an intense structured emission. The emission from the Pt(php)Cl+ and related derivatives exhibit pronounced vibrational structure and a mixed 3π-π/ 3d-π* orbital parentage. Upon substitution of methyl groups onto the 1,10-phenanthroline backbone a dramatic increase in emission and lifetimes are observed. The next chapter examines the DNA binding interactions of the Pt(php)Cl + and the Pt(5,6-Me2)Cl+ complexes (where 5,6-Me2-php = 2-(2′-pyridyl)-5,6-dimethyl-1,10-phenanthroline). The Pt(php)Cl+ and Pt(5,6-Me2-php)Cl+ complexes are shown to bind via intercalation and covalently to DNA depending upon the base pair composition. The novel photophysical properties of the Pt(II) complexes have proven to be a useful tool in ascertaining the binding interactions to different types of DNA. The slightest change in the environment for the Pt(php)Cl+ and Pt(5,6-Me2-php)Cl + has profound impacts on the photophysical properties. Chapter 3 studies the structural and photophysical properties of Cu(NN) 2+ systems in the solid state. This chapter describes the crystal and molecular structures of a series Cu(NN)2 +-containing systems along with spectral data obtained from the solids themselves. The results show that a flattening distortion can have a large impact on the spectroscopic properties of a Cu(NN)2+ system, whereas a typical rocking distortion has comparatively little effect. This is the first report of emission from a bis(phenanthroline)copper(I) system that does not have bulky substituents in the 2 and/or 9 positions of the ligand.
Degree
Ph.D.
Advisors
McMillin, Purdue University.
Subject Area
Chemistry|Biochemistry
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