Novel roles for ferrocene derivatives in molecular recognition

Date of Award




Degree Name

Doctor of Philosophy (Ph.D.)

First Committee Member

George W. Gokel, Committee Chair


The first chapter deals with the syntheses and characterization of the cation binding properties of several ferrocenyl ionophore compounds. Special interest was given to ferrocenydimethyl-(2.2) -cryptand which possess extraordinary cation binding abilities. The cation-ionophore interactions of this compound were studied by $\sp1$H, $\sp{13}$C, and $\sp{23}$Na NMR spectroscopy, UV-Visible spectroscopy, fast atom bombardment mass spectroscopy, X-ray analysis, cyclic voltammetry, and ion selective electrode techniques. Evidence for the role of iron as a donor group was found using these techniques. The strong cation stabilizing properties of ferrocenyldimethyl-(2.2) -cryptand allowed for the first time the use of a redox switchable ionophore in the determination of cations in water.In chapter two we discuss the syntheses and properties of a novel family of molecular receptors designed to bind small molecules. The X-ray analysis of the structure of one of the analogs show some degree of preorganization. $\sp1$H NMR techniques were employed to assess the extent of complexation exhibited by these receptors. In these molecules the ferrocene is used as an "atomic ball bearing" because of the small rotation energy of the cyclopentadiene rings.In the last chapter we discuss a novel family of ferrocenyl surfactants. Ferrocene is a neutral molecule of low polarity, however, when oxidized it becomes a ferrociniun cation. This positively charged molecule can serve as the polar head in our family of amphipathic compounds. It was demonstrated that ferrocenylmethyl dihydrocholesteryl ether did not aggregate when the molecule was in its neutral state, however, once oxidized it aggregated into irregular multilamellar vesicles as determined by electron microscopy and dynamic light scattering experiments. This constitutes the first case of electrochemically switchable vesicles.


Chemistry, Organic; Engineering, Chemical

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