{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/29325"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/29325","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Exohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenes","abstract":"This 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.","abstract_html":"This 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 &lt;i&gt;(D&lt;sub&gt;5h&lt;/sub&gt;)&lt;/i&gt; 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)&lt;sub&gt;~10&lt;/sub&gt;(O)&lt;sub&gt;~10&lt;/sub&gt;, 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 &lt;i&gt;D&lt;sub&gt;5h&lt;/sub&gt;&lt;/i&gt; 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.","abstract_has_math":false,"creators":["Iezzi, Erick B."],"institution":"Virginia Tech","degree_name":"Ph. D.","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":["Dorn, Harry C."],"committee_members":["Deck, Paul A.","Tanko, James M.","Long, Timothy E.","Hanson, Brian E."],"year":2003,"date_issued":"2003-10-14","date_published":"2003-10-14","updated_at":"2026-07-22T22:19:33Z","subjects":["endohedral","metallofullerene","scandium nitride","X-ray contrast","functionalization"],"languages":[],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-10212003-130521"],"render_values":[{"text":"etd-10212003-130521","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10919/29325","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeechair","label":"Committee Chair","values":["Dorn, Harry C."]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Deck, Paul A.","Tanko, James M.","Long, Timothy E.","Hanson, Brian E."]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Iezzi, Erick B."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2014-03-14T20:17:31Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2014-03-14T20:17:31Z","2004-10-24"]},{"key":"dc:date.issued","label":"Date","values":["2003-10-14"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Tech"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["endohedral","metallofullerene","scandium nitride","X-ray contrast","functionalization"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-10212003-130521"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/29325"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This 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."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D."]},{"key":"dc:title","label":"Title","values":["Exohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenes"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Dorn, Harry C."],"dc:contributor.committeemember":["Deck, Paul A.","Tanko, James M.","Long, Timothy E.","Hanson, Brian E."],"dc:contributor.department":["Chemistry"],"dc:creator":["Iezzi, Erick B."],"dc:date.accessioned":["2014-03-14T20:17:31Z"],"dc:date.available":["2014-03-14T20:17:31Z","2004-10-24"],"dc:date.issued":["2003-10-14"],"dc:description.abstract":["This 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."],"dc:description.degree":["Ph. D."],"dc:identifier.other":["etd-10212003-130521"],"dc:identifier.uri":["http://hdl.handle.net/10919/29325"],"dc:publisher":["Virginia Tech"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:subject":["endohedral","metallofullerene","scandium nitride","X-ray contrast","functionalization"],"dc:title":["Exohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenes"],"dc:type":["Dissertation"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Ph. D."],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:19:33Z"}