Methodology and host-guest chemistry of organic and organometallic compounds

Reactions of C60C16, C60Br8, or C60(NO2)6 with arene and alkene substrates under mild conditions afford primarily monochlorinated, monobrominated, or mononitrated organic products in high yield for the arene substrates, often with greater selectivity and reactivity than with traditional halogenation or nitration methods for both arene and alkene substrates. The reactions have the advantages of high stereoselectivity and facile removal and recovery of [60]fullerene. No metal catalysts, gases, or harsh acids are required. These results demonstrate the versatility of the functionalized fullerenes as new synthetic tools for organic synthesis.;The next aspect of research focused on host-guest chemistry of fullerenes. The emphasis of this research was on designing small aromatic molecules and studying their interactions with fullerenes through mass spectrometry. Using mass spectrometry it could be determined if the host compounds had an affinity for the fullerene, by the appearance of a mass ion peak at the combined molecular weight of both the host compound and fullerene.;Synthesizing several organometallic compounds and examining their interactions through X-ray crystallography also explored host-guest chemistry with fullerenes. The class of compounds used was tetraazaannulene compounds for their large pi system and concave structure. The concave structure of these compounds allowed the host to complement the curvature of C60. Host-guest chemistry examined by X-ray crystallography not only gives insight into the interaction between the host and guest, but also has the application of being used as a cocrystallizing agent. The tetraazaannulene compounds have demonstrated a remarkable ability to order the fullerene in the cocrystallization, which is often a problem in many fullerene crystal structures.;The synthesis and crystallization of numerous tetraazaannulene compounds have been used to gain insight into a wide variety of secondary interactions. Various derivatives that contain additional phenyl rings, halogens and nitro groups were synthesized and how these functional groups affect the crystal structure was examined.;Porphyrins have recently received much attention for their potential as hosts for fullerenes and have frequently been used as cocrystallizing agents. Herein I describe the synthesis of various meso-Schiff-base octaethylporphyrins. Reactions of meso-formyl octaethylporphyrin (f-m-OEP) with amines either as the substrate or with 1,3-diaminopropane as the linker have led to a library of new Schiff-base porphyrins. These schemes allow for convenient synthesis of large macromolecules.;The synthesis and characterization of Co and Rh organometallic compounds demonstrated several intriguing properties. The Schiff-base ligand was synthesized by using 2-hydroxy-1-naphthaldehyde and 1-aminoadamantane in ethanol. These large organic substituents made the organometallic complexes more soluble in organic solvents. The steric effects of the adamantane unit had a propensity for the trans conformation in the crystal structures, thus affording some control over the chelation of the ligands to the respective metals.