Title

The synthesis and study of molecular receptors containing ferrocene group

Date of Award

1995

Availability

Article

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Chemistry

First Committee Member

George W. Gokel, Committee Chair

Abstract

The ferrocene subunit has been used in the design and production of a family of small molecular receptors that have a molecular cleft which varies in size, shape and electron richness. The following characteristics of ferrocene were utilized in building molecular receptors and ionophores. (1) the ferrocene system is capable of undergoing oxidation at the iron atom to produce a ferrocinium species in which iron is formally 3$\sp+$, which offers an additional recognition in altering the coulombic forces present in the complexation. (2) The two cyclopentadiene rings are active aromatic rings to electrophilic substitution reactions, which provides an easy way to attach functional groups. (3) the ferrocene inter-ring distance is 3.25A. This provides the proximity between the binding site and the redox-active center. (4) The two cyclopentadiene rings can easily rotate relative to each other, which provides certain degree of flexibility to achieve convergent conformation to accommodate to different substrates' size.In the first chapter, the synthetic approaches, binding constants and structural information revealed by X-ray, nuclear magnetic resonance, and ionization constants are discussed.In the second chapter, lariat ethers containing the ferrocene subunit were synthesized. Binding of Na$\sp+$ and Ca$\sp{2+}$ by these compounds were studied by ion selective electrode and NMR techniques. The results were compared to those determined by study of other lariat ethers. The design and synthesis of ionophores containing multi redox-active center and the receptors towards anion recognition were also discussed.

Keywords

Chemistry, Organic

Link to Full Text

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