Novel organic materials from efficient synthetic methods

Utilizing a key 1,3-dipolar cycloaddition, a pyrrolo-pyridazine derivative with high fluorescence efficiency was developed. A systematic method of determining electronegativity of β-diketone ligands was described from analyzing its fluorescence quantum yield. Further synthetic efforts extended its utility to contain chelation sites for luminescent metals. A notable successful metal chelates to various ligands with europium afforded the expected change of fluorescence from blue, resulting from the ligand, to red, resulting from europium.; Dibenzocyclooctadiene-diyne is an interesting strained tricyclic hydrocarbon for which an efficient synthesis is not available. Utilizing new methods as well as optimizing old methods, we were able to develop two synthetic routes to our target in 40–45% overall yield in each case. This material was utilized to develop novel cyclophanes, conducting polymers, and curved graphitic surfaces.; A tetra-benzannelated cyclophane was developed in two efficient synthetic processes. We showed that benzannelation increases the strain of the stacked aromatic system as shown by its rapid reactivity with TCNE. A mono-adduct was isolated and characterized in which the strain of the system could be relieved by the addition.; Conducting polymers from dibenzocyclooctadiene-diyne were developed bearing both a linear structure as well as a ladder structure. Linear polymers could be made in the thermal polymerization of the target monomer to produce poly(indenoindene) which showed semi-conducting properties. Ladder structures, utilizing the bis-dienophilic nature of the target diyne, were developed by trapping a highly reactive bis-furan intermediate followed by aromatization to the conducting polymer. This material also showed semi-conducting properties.; Curved graphitic surfaces were developed with the anticipation of interacting with curved substrates, such as nanotubes and fullerenes. An efficient synthesis of these structures is described as well as an interesting red fluorescent by product. By MALDI-MS, we determined that over-oxidation and chlorination had occurred in a key cyclization process which led to this interesting hydrocarbon.