Molecular and Electronic Structure Studies on Binuclear Manganese Complexes
Kamber, Nahrain E.
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The goal of this project is to further explore the structural and electronic characterization of various homo-and heterobinuclear manganese complexes bound by a macrobicyclic ligand (macrobicycle hereafter). The symmetrical, relatively inflexible organic ligand environment completely encapsulates two metal ions while binding the ions in close proximity. The ligand provides an environment in which the magnetic and electron transfer properties free of direct solvent interaction are investigated. Most of the compounds prepared in this study have been characterized by previous Kalamazoo College students via infrared and electronic absorption spectroscopy, solution and solid state magnetic susceptibility, electrochemistry, and three of them by X-ray crystallography. This project further investigates these manganese complexes by additional infrared, Raman, and electronic absorption spectroscopy (lR, RS and ES), electronic paramagnetic resonance spectroscopy (EPR), and more detailed analysis of Xray crystallographic results. The clathrochelate ligand employed in this study was introduced in 1985 by W. Marritt, D. Hendrickson, R. Gagne, and E. Sinn. I Clathrochelate complexes are complexes in which a metal ion is completely encased in a ligand cage. The ligand is derived from the condensation of 3 equivalents of 2, 6-diformyl-4-methylphenol (diaIH) and 2 equivalents oftris(2-aminoethyl)amine (trenH6). Figure I shows formation of the axial macrobicyclic-ligand coordination complex.