A SYNERGISTIC SYNTHETIC, SPECTROSCOPIC AND COMPUTATIONAL APPROACH TO THE DESIGN OF ORGANOMETALLIC PLATFORMS FEATURING LINEARLY FUNCTIONALIZED AZULENIC AND BIAZULENIC MOTIFS

Abstract

While there is great interest in using small organic molecules in everything from organic light emitting diodes to charge transport in molecular electronics, finding the right scaffold for development has posed substantial challenges. Linear azulenic motifs have proven the ability to delocalize electrons and demonstrate unique photoluminescence properties. Continuing the development of functionalized azulenes in the Barybin group, this dissertation describes the explorations into mercapto- and isocyano- azulenes and biazulenes. With a diverse toolkit, the dynamics, materials, energy, reactivity, and spectroscopy of these systems have been described. In Chapter 1, the preparation, X-ray crystal structures, theoretical models, reactivities, and photoluminescent behavior of the mercapto-azulene ligands and gold(I) complexes involving 2- and 6-azulenyl thiolate motifs are discussed. These novel compounds constitute attractive platforms for developing new photoluminescent materials and, possibly, metallopharmaceuticals. In Chapter 2, 2,6-dimercapto-1,3-diethoxycarbonylazulene, a rare example of an unsymmetric dimercaptoarene, was computationally determined to be an excellent system to undergo regioselective metallation. The [Ph3PAuI] metalated complex was shown to have very dynamic behavior using NMR studies. This complex constitutes a unique unsymmetric platform for probing the exchange of gold-bound thiolates within a single compound. In Chapter 3, linear, functionalized 6,6'-biazulenyl's were synthesized in excellent yields. Unusual 2e- redox behavior was addressed electrochemically and computationally. The reduced anionic and dianionic states were explored using theoretical, EPR, and UV-Vis-NIR methods.