This dissertation investigates the preparation and electrochemical studies on a series of novel redox active hybrid dendrimers. The author also describes cucurbit[8]uril (CB8) mediated dendrimer self-assembly and their size selection by applying external electrochemical stimulus. In addition to this, a series of redox active, carboxylic acid terminated dendrimers were deposited onto indium tin oxide (ITO) surfaces. The surface interactions between the dendrimers and the metal oxides were characterized by electrochemical, spectroscopic, and atomic force microscopic methods. Additionally, the author describes molecular recognition behavior studies between several redox active guests and cucurbit[7]uril (CB7) in non-aqueous media. Furthermore, the author also describes the preparation and electronic communication studies on a series of bisferrocenylamino triazine derivatives. Three chapters of this dissertation deal with dendrimer applications in several different topics. A general introduction to dendrimers is given in Chapter I, including a short history, dendrimer structural features, synthetic methodologies, and also including their general applications on several different topics. Chapter II describes the preparation and characterization of a series of novel redox active hybrid dendrimers. These dendrimers consist of a ferrocenylamino nucleus and two series of popular dendrons (Fréchet and Newkome type). Interestingly, the microenvironment surrounding the redox residues is finely adjustable by varying the size of these two types of dendrons. Chapter III describes the molecular recognition studies with selected redox active guests and the macrocyclic host CB7 in non-aqueous media. The extremely strong host-guest interaction between CB7 and ferrocenylmethyl-trimethylammonium (FA) in aqueous media experiences a substantial thermodynamic stability loss when transferred to non-aqueous media. In stark contrast to this, the binding behavior between CB7 and the dicationic guest methyl viologen (MV) exhibits less sensitivity to environmental variation. Furthermore, the electrochemical studies were performed under non-aqueous media. In general, host CB7 encapsulation of these redox active guests in non-aqueous media induces different electrochemical behavior compared to that of aqueous media. For instance, the cyclic voltammetric response of CB7 encapsulated FA in DMSO exhibit substantial cathodic potential shift, which is opposite to the behavior in aqueous media. Chapter IV describes CB8 mediated dendrimer self-assembly. A new series of pi-donor containing Newkome type dendrimers were synthesized. These pi-donor containing dendrimers are found to form stable ternary charge transfer complexes with another series of pi-acceptor (viologen) containing dendrimers. Furthermore, one electron reduction of the viologen residue disrupts the charge transfer complexes and leads to the assembly of viologen radical cation dimmers. And, thus, may result in substantial size selection between these two types of dendrimer assemblies. Chapter V describes the exploration of a series of redox active dendrimers bearing multiple carboxylic acids as surface anchoring groups to attach onto the optical transparent semiconductor material ITO coated glass surfaces. The dendrimer derivatized ITO slides were further prepared as working electrodes, and the subsequent electrochemical studies revealed that these dendrimers strongly adsorb onto ITO surfaces. Especially, the ITO electrodes treated with the second generation dendrimer exhibit rather stable electrochemical behavior. The surface coverages of ITO electrodes treated with dendrimers were estimated by current integration. Atomic force microscopic studies provided insights on surface topographical variation before and after the dendrimer deposition. Infrared spectroscopic studies further revealed the chemical interactions between dendrimer carboxylic acid groups and the metal oxide surfaces. Chapter VI describes the preparation of a series of triazine based bisferrocenylamino derivatives. Variable 1H-NMR and 13C-NMR spectroscopic studies clearly indicate that these bisferrocenylamino triazine derivatives exhibit rotamerization phenomena. And, the rotamer coalescence temperatures are mediated by the third substituent group. The X-ray crystallographic analyses disclose the partial double bond character between the amino nitrogen and the triazine carbon, which reveal the structural proof behind the rotamerization phenomena. Furthermore, electrochemical experiments are performed under two sets of experimental conditions. No electronic communication is observed when using the traditional tetrabultylammonium hexafluorophosphate (TBAPF6) as supporting electrolyte. In stark contrast to this, electronic communication between the bisferrocenyl residues is observed when using tetrabultylammonium tetrakis(pentafluorophenyl)borate (TBAB(C6F5)4) as supporting electrolyte. Surprisingly, the electronic communication strength can be mediated by a third substituent group. Computational studies provide insights into the molecular geometry and electronic structure of the mixed valence species. By combining the supporting electrolyte dependant electronic communication behavior, near-IR spectroscopic studies and the computational results, we conclude that, the electronic communication between the bisferrocenyl residues in these investigated triazine derivatives occurs through space metal-metal interactions.
| Identifer | oai:union.ndltd.org:UMIAMI/oai:scholarlyrepository.miami.edu:oa_dissertations-1175 |
| Date | 14 December 2008 |
| Creators | Wang, Wei |
| Publisher | Scholarly Repository |
| Source Sets | University of Miami |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | Open Access Dissertations |
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