Date of Award

2001

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Robert Strongin

Abstract

Interest in the fullerenes is due, in large part, to the fact that they represent the third major form of carbon, following graphite and diamond. We have investigated synthetic methods towards the creation of new carbon molecules derived from the fullerenes. The sought-after dimeric carbon fullerene derivative, C122, was successfully synthesized and isolated for the first time in modest yield from a complex reaction mixture. The all-carbon molecular allotrope was prepared via the new reaction of C60 with atomic carbon in solution. Atomic carbon was produced via the known thermolytic decomposition of diazotetrazole. Future work that could emanate from these studies includes the development of new fullerene chemistries toward the production of oligomeric and coalesced (cage-merged) C60 derivatives. Towards these ends, the first Suzuki coupling reaction of a methanofullerene was performed. Model reaction conditions, in keeping with strong literature precedent for other systems, were developed. Product characterization is ongoing. This work should lay the groundwork for future efforts in the area of methanofullerene coupling reactions. Studies of the reaction of other azoazole heterocycles (i.e., congeners of diazotetrazole) have begun in order to probe and broaden the scope of the reaction of these molecules with the fullerenes. The reaction of diazodicyanoimidazole with C60 is described along with detailed product isolation analysis. Apart from the analogy to our diazotetrazole reaction, these efforts appear to have led to the formation of new fullerene adducts which potentially embody more electron accepting character than the parent fullerenes. Fullerene derivatives with enhanced electron accepting character are relatively rare. They help serve to create analogies between fullerene and benzene chemistries. They may find application in biology and materials science. Studies of other relatively large benzenoid systems are described. The cyclic tetramers of resorcinol, the resorcinarenes were discovered by our research group to promote solution color changes in the presence of various sugars. This is a potentially highly practical result with possible applications in diagnostics and industrial product analysis. The resorcinarenes were discovered by von Bayer in 1872 and were shown to exhibit colorimetric effects at that time; however, no one has investigated the origin of these effects nor probed their utility. Herein initial studies towards HPLC chromatographic isolation of colored materials from resorcinarene solutions are described as well as the mass spectrometric analysis of the adducts of resorcinarenes with various analytes.

ISBN

9780493271873

Pages

79

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