Access Type

Open Access Dissertation

Date of Award

January 2012

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry

First Advisor

Claudio N. Verani

Abstract

The integration of amphiphilic properties into transition metal coordination systems is a pertinent step toward the development of candidate metallosurfactant precursors for the formation of responsive monolayer films. This concept is intended to preserve the solution-observed redox, spectroscopic, and magnetic responses onto solid surfaces for potential application. Selected metal ions and various ligand designs are investigated to address the effect of coordination and protonation preferences on amphiphilic behavior, the aspects of new modular approaches for Langmuir film precursors of differentiated topologies to extend amphiphilicity and redox behavior, and the introduction of photosensitizing properties into electroactive metallosurfactant precursors. In an attempt to enhance the redox response of our current phenolato-based ligand scaffolds, rich multielectronic ligand-centered redox reactivity is established with the amino-catecholate functionality and will be incorporated into prospective ligand schemes. A concerted effort merges the comprehensive synthetic, electrochemical, spectroscopic, and photophysical evidence, film formation methods, and computational techniques.

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