Synthesis, Characterization, and Reactivity of Cross-Conjugated Frameworks

ABSTRACTVICTORIA LEIGH HAMILTON. Synthesis, Characterization, and Reactivity of Cross-Conjugated Frameworks. (Under the direction of MARKUS ETZKORN)Molecules with cross-conjugated -systems possess unique structures and reactivity due to their distinctive form of conjugation that fundamentally differs from the isomeric through conjugated systems by atom connectivity. Many of the organic compounds that played a vital role in the development of industrial organic chemistry are cross-conjugated systems or were transformed to cross-conjugated organic salts (e.g., dyes such as indigo). Our larger goal to synthesize novel cross-conjugated frameworks with potential for biological or materials applications, depended on a preparative scale synthesis of necessary precursors. We prepared a small library of arene-substituted isoindanone derivatives that necessitated optimization of synthetic routes according to electronic demands of the individual systems. Reproducible routes were actualized to afford multigram quantities of these compounds as the necessary precursors to the polycyclic scaffolds targeted herein. Through this project we have established reliable protocols to novel isoindenone dimers that are synthetically intriguing substrates, which may be utilized to further investigate the electronic structure of their fleeting-intermediate monomers. Other intermediates, i.e. dibenzo[b,e]fulvalenes, have provided access to novel bimetallic complexes through ligand association reactions with appropriate transition metal carbonyl moieties. The introduction of arene substituents that are electron-donating or electron-withdrawing provided electronic contrast between these structures.