Title: Azobenzenes
Description: This dissertation describes the synthesis of novel, small molecule building blocks and the phenomena that are revealed when they are studied in unusual environments. Chapter 1 is divided into two sections, serving as introductions for chapters 2-3 and 4-5 respectively. The first section introduces the scanning tunneling microscope break junction (STM-BJ) as a new environment for reaction chemistry. Chapter 2 describes a truly single molecule reaction in which azobenzenes are formed in the STM-BJ one molecule at a time. Chapter 3 describes an electrostatically driven Ullmann coupling reaction of biphenyl iodides in the STM-BJ. In contrast to the reaction described in chapter 2, this reaction occurs throughout the solution in the presence of an electric field that surrounds the nanoelectrodes. The second half of chapter 1 provides a primer on the photoisomerization of azobenzenes, a class of small molecule dyes whose unique photochromic profile and switchable properties have been exploited across a wide range of fields.

Chapter 4 introduces azobenzenes as photoswitchable ligands on superatomic clusters. Chapter 5 details the phenomenon and mechanism of white light driven rolling of Cu(I) isocyanoazobenzene crystals. Finally, chapter 6 is a self-contained research project. It details an organocatalytic O₂-coupled oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes.