Modification of Metal Phosphonate Monolayers and the Effect on Interfacial Organization and Translational Dynamics

Self-assembled monolayers (SAMs) are used widely for surface modification due to the range of chemical structures available and the comparative ease of synthesis. In particular, metal-phosphonate and metal bisphosphonate (MP) films have received attention for several decades. MP films were first described using zirconium but have since been expanded to include other metals including many group II metals, first and second row transition metals, and many lanthanides, with a variety of oxidation states represented. While the structural properties of MP films have been characterized thoroughly and reported, the dynamics within MP film have not received much attention. The focus of this dissertation is on determining the surface organization and translational dynamics of MP monolayers. Due to the large variability in MP films, modifications of traditional ZP monolayers and the effects of constituent dynamics are reported here. The effect of metal ion charge and identity on the metal ion complexation equilibria and exchange kinetics, and surface organization were investigated. Many reported MP monolayers are formed using an ,-alkanebisphosphonate, however this constituent can be easily substituted or modified for a variety of applications. Reported here is the effect of constituent modification on the constituent exchange dynamics and consequent translational mobility within MP monolayers.