Understanding nanocomponentry: The design, synthesis and testing of fullerene- and carborane-functionalized machines and devices

Abstract

"Nanocomponentry" is defined as a collection of nano-sized molecules or units that can be chemically assembled in various configurations to form structures intended to do work at the nanoscale. C60 fullerenes and carboranes are both spherically in shape and possess a variety of unique properties. Described here is the design, synthesis, and testing of molecules, with the emphasis on the use of C60 and carborane and their related chemistries, to help understand nanocomponentry. In chapter 1, in a continuation of the nanocar project (single molecular surface-rolling nanomachines comprised of spherical fullerene wheels, freely rotating alkynyl axles and a molecular chassis), a series of fullerene-based nanomachines were designed and synthesized to further our understanding of the directional control and surface-rolling capabilities of the series. Chapter 2, azobenzene moieties were studied to introduce a "handle" for photochemically controlled nanomachines and devices. The presence of fullerenes in the systems had an effect on the photoisomerization of the molecules. To observe the effects of the fullerenes, wheels produced from p-carboranes were introduced. In chapter 3, because of the advantageous properties, several nanovehicles were synthesized using p-carboranes as the wheel system. In chapter 4, the idea of an assembly line to produce nanovehicles is explored. In chapter 5, several imaging techniques were explored in order to address issues such as molecular resolution and substrate compatibility. In chapter 6, as an initial step toward exploring the transparency phenomena of the images of fullerene-functionalized devices and nanomachines from the past STM experimentation, a non-symmetric OPE was synthesized, where solublizing dodecyl groups were removed on one end of the OPE. In chapter 7, a series of fullerene-derivatized OPEs was synthesized for potential use in electronic devices. The products were terminated with thiols and protected thiol alligator clips to enable surface assembly on metallic surfaces such as gold. Throughout my career in the Tour group, I have been active in generating computer graphic images of my own projects as well as images for other projects within our group. In chapter 8 I present some of the notable illustrations I generated that were published in some form of media.