Date of Award

8-2008

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Chemistry

Advisor

Echegoyen, Luis

Committee Member

Rao , Apparao M.

Committee Member

McNeill , Jason

Committee Member

Kholodenko , Arkady

Abstract

The discovery in 1985 of fullerenes combined with the development of STM beginning in 1981 is credited as the starting point of the current nanoscience revolution. Endohedral fullerenes, discovered shortly after, have drastically different electronic properties when compared with the empty fullerenes. This dissertation has as its central focus the synthesis and electronic properties of endohedral metallofullerenes and other endohedral nanostructures.
The opening two chapters give a brief background of the discovery of fullerenes. A comprehensive literature list is given for the various families of trimetallic nitride endohedral fullerenes as well as other large endohedral metallic cluster fullerenes. Finally, a brief overview of the discovery and differentiation of the types of carbon nano-onions is presented. The second chapter presents the relevant theory and background for both EPR spectroscopy and electrochemistry.
Chapter 3 spotlights Sc3N@C80: its synthesis and electronic characterization by electrochemistry and EPR spectroscopy as well as its change in behavior upon the addition of functional groups onto the cage.
Chapter 4 expands the previous chapter's data to other M3N@C80 and compares and contrasts with the analogous behavior of Sc3N@C80.
Chapter 5 describes the attempted electrochemical synthesis of an endohedral lithium open fullerene complex, Li+@OF, and its characterization.
Chapter 6 reassigns the EPR data formerly attributed to the endohedral fullerene Cu@C60 to a different and previously characterized organic molecule.
Chapter 7 gives a strategy for the synthesis of the first 'super-endohedral' nanostructures CNO@CNT.
Chapter 8 attempts a prediction of the next potentially significant direction in endohedral fullerene composition and structure.
The appendices at the end of the dissertation contain brief reports on unrelated work attempted or completed during the course of this degree. Various electrochemical and EPR studies on organic molecules are presented.

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