Proton transfer effects on the redox properties of dinuclear and multinuclear ferrocene amines
Date of Award
Doctor of Philosophy (Ph.D.)
First Committee Member
Angel E. Kaifer - Committee Chair
In this dissertation, the author describes the synthesis and characterization of fourteen novel dinuclear and polynuclear ferrocene amines whose redox behavior is strongly affected by the protonation state of the molecule. The study of the compounds was carried out by voltammetric techniques, X-ray diffraction and 1H-NMR spectroscopy. The most interesting feature discovered in these molecules is the correlated nature between proton and electron transfer to induce dramatic changes on the electrochemical behavior of such compounds.Chapter one briefly describes the significance of the coupling between electron and proton transfer to generate sophisticated chemical and biochemical functions and highlights the importance of synthesizing molecules capable of transferring both proton and electrons.Chapter two presents voltammetric evidence of how the electronic communication between two equivalent ferrocene centers (dimer) can be modulated by protonation or N-methylation of the amine nitrogen.Crystallographic data indicate that such behavior in solution seems to be correlated with the systematic structural pattern observed in the solid state.Chapter three is a natural extension of chapter two showing a modulation of the electronic interaction between two equivalent ferrocene units but in this case caused by structural changes using dendritic motifs attached to the ferrocene dimer.Chapter four shows electrochemical evidence indicating how partial protonation or N-methylation of nitrogen centers spread along the polyferrocene molecule allows the selection of different redox potentials to transfer electrons.
Alvarez, Julio Cesar, "Proton transfer effects on the redox properties of dinuclear and multinuclear ferrocene amines" (2000). Dissertations from ProQuest. 1668.