Exohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenes

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dc.contributor.authorIezzi, Erick B.en
dc.contributor.committeechairDorn, Harry C.en
dc.contributor.committeememberDeck, Paul A.en
dc.contributor.committeememberTanko, James M.en
dc.contributor.committeememberLong, Timothy E.en
dc.contributor.committeememberHanson, Brian E.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T20:17:31Zen
dc.date.adate2003-10-24en
dc.date.available2014-03-14T20:17:31Zen
dc.date.issued2003-10-14en
dc.date.rdate2004-10-24en
dc.date.sdate2003-10-21en
dc.description.abstractThis dissertation addresses the exohedral cage functionalization and potential applications of the Sc₃N@C₈₀ and Sc₃N@C₇₈ trimetallic nitride endohedral metallofullerenes. In addition, this dissertation discusses miscellaneous research that is relevant to the aformentioned metallofullerenes and their applications, such as the discovery of a new cage isomer <i>(D<sub>5h</sub>)</i> of Sc₃N@C₈₀, the synthesis of Lu₃N@C₈₀ as a novel X-ray contrasting agent, and the synthesis of Sc₃¹⁵N@C₈₀ with ¹⁵N₂ gas. The first derivative of Sc₃N@C₈₀ was synthesized by functionalizing the exterior of the cage via a [4 + 2] cycloaddition reaction with a ¹³C-labeled intermediate. Addition occurred across the [5,6] ring-juncture of the cage to form a mono-adduct, which has a mirror plane of symmetry as observed from the time-averaged ¹³C NMR spectrum. The structure of the mono-adduct was confirmed by X-ray crystallography. Diethyl and dibenzyl malonate adducts of Sc₃N@C₈₀ were synthesized, in addition to a ¹⁵N-labeled terminal amine derivative. Water-soluble metallofullerenols, Sc₃N@C₈₀(OH)<sub>~10</sub>(O)<sub>~10</sub>, were synthesized from polyanionic intermediates. The Sc₃N@C₇₈ metallofullerene was derivatized with a ¹³C-labeled reagent to afford mono-, di- and tri-adducts. A single structural isomer of the mono-adduct was found, while several isomers of the di- and tri-adducts were observed by HPLC. ¹³C and ¹H NMR data of the mono-adduct support a structure that results from addend addition to an asymmetric site on the C₇₈ carbon cage. The HPLC isolation and characterization of Lu₃N@C₈₀ is discussed. When irradiated with X-rays, Lu₃N@C₈₀ provided a small level of contrast that can only be attributed to the large atomic number (Z) of the lutetium atoms. Mixed-metal species that contains gadolinium and lutetium or holmium and lutetium could be employed as multifunctional contrasting agents for X-ray, MRI and radiopharmaceuticals, thereby eliminating the need for three separate agents. A new cage isomer of the Sc₃N@C₈₀ metallofullerene was synthesized and partially isolated by HPLC. This carbon cage possesses <i>D<sub>5h</sub></i> symmetry, as indicated by the time-averaged six line ¹³C NMR spectrum with a 1:2:2:1:1:1 ratio. The internal metal-nitride cluster of Sc₃N@C₈₀ was synthesized with a ¹⁵N-label for studying the motion(s) of the cluster (within the carbon cage) at various temperatures using ¹⁵N NMR spectroscopy.en
dc.description.degreePh. D.en
dc.identifier.otheretd-10212003-130521en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-10212003-130521/en
dc.identifier.urihttp://hdl.handle.net/10919/29325en
dc.publisherVirginia Techen
dc.relation.haspartE.B.Iezzi-PhD-dissertation.pdfen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectendohedralen
dc.subjectmetallofullereneen
dc.subjectscandium nitrideen
dc.subjectX-ray contrasten
dc.subjectfunctionalizationen
dc.titleExohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenesen
dc.typeDissertationen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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