Title

Dendritic and metallic nanoassemblies

Date of Award

2005

Availability

Article

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Chemistry

First Committee Member

Angel E. Kaifer, Committee Chair

Abstract

This dissertation investigates the synthesis and electrochemical properties of dendrimers and their supramolecular interactions with different host molecules. Additionally, the author describes the self-assembly of metallic nanostructures by wire-like bis-ruthenium metallaynes. These studies were carried out by a wide range of techniques including, cyclic voltammetry, NMR spectroscopy, mass spectroscopy, UV-vis spectroscopy and TEM.Chapter one is a brief introduction into the science of dendrimers and describes the evolution of these molecules from mere intellectual curiosities to their present emerging applications which take advantage of their unique properties. The potential of dendrimers is limitless and this field is still relatively young.Chapter two describes the synthesis and electrochemical characterization of dendrimers which have electroactive cores and their supramolecular interaction with the host molecule CB7. The electroactive core served as a probe for the dendritic microenvironment and gave information about the conformational changes of these dendrimers. Additionally, the electroactive moiety on these molecules also served as a probe to investigate the host binding properties of the CB7 molecule and reveals the importance of electrostatic forces in the modes of binding of CB7.Chapter three describes the interaction of electroactive hydrophobic dendrimers with a resorcinarene host molecule. This interaction was found to increase with dendrimer generation and this binding was aided by the polyvalence of dendrimers and cooperativity of multiple non-covalent interactions including hydrogen bonding and cation-pi interactions.Chapter four describes the use of wire-like ruthenium complexes as tethers for self-assembly of metallic nanostructures. The transition metal backbone was previously shown to aid electronic communication between the ends of conjugated systems. This work demonstrates that wiring of components can be achieved by self-assembly.

Keywords

Chemistry, Analytical; Chemistry, Organic

Link to Full Text

http://access.library.miami.edu/login?url=http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:3198740