{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/77994"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/77994","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Preparation, Separation, Characterization and Hydrogenation of Endohedral Metallofullerenes","abstract":"Endohedral metallofullerenes (EMFs) have attracted increasing attention during past decades due to their novel structures and potential applications in a variety of fields such as biomedical applications and molecular electronics. This dissertation addresses the structural characterization and hydrogenation of EMFs. A family of novel large cage yttrium-based TNT EMFs Y₃N@C₂ₙ (n=40-44) was prepared, separated, and structurally characterized for the first time. The structure of Y₃N@C₂ₙ (n=40-44) is proposed by the experimental and computational ¹³C NMR studies. The first ⁸⁹Y NMR results for Y₃N@<I>Iₕ</i>-C₈₀, Y₃N@<I>Cₛ</i>-C₈₄ and Y₃N@<I>D₃</i>-C₈₆ reveal a progression from isotropic to restricted (Y₃N)⁶⁺</sup> cluster motional processes. The di-metallic EMF Y₂C₉₄ is distinguished as a metal-carbide based EMF, Y₂C₂@<I>D₃</i>-C₉₂. The carbide within the cage is successfully detected by ¹³C NMR. The scalar J<sub>Y-C</sub> coupling between the yttrium atoms and the C₂ unit within the C₉₂ cage is successfully observed, suggesting the C₂ unit rotates rapidly around the yttrium atoms. Two paramagnetic endohedral metalloheterofullerenes, Y₂@C₇₉N and Gd₂@C₇₉N, were also synthesized and characterized. The EPR study demonstrated that the spin density is mainly localized between the two metallic ions. A spin-site exchange system could be constructed between Y₂@C₇₉N and the organic donor TMPD. Being a unique paramagnetic material, Gd₂@C₇₉N displays an unusual stability over a wide temperature range, which could be very useful in optical and magnetic areas. Functionalization of EMFs is another point of interest in this dissertation. Hydrogenated Sc₃N@C₈₀ was synthesized and characterized. Our study demonstrated that the Sc₃N@C₈₀ can be fully hydrogenated and the pristine Sc₃N@C₈₀ can be recovered from Sc₃N@C₈₀H₈₀ after being heated in vacuum. The hydrogenated EMFs could be potential hydrogen storage materials.","abstract_html":"Endohedral metallofullerenes (EMFs) have attracted increasing attention during past decades due to their novel structures and potential applications in a variety of fields such as biomedical applications and molecular electronics. This dissertation addresses the structural characterization and hydrogenation of EMFs. A family of novel large cage yttrium-based TNT EMFs Y₃N@C₂ₙ (n=40-44) was prepared, separated, and structurally characterized for the first time. The structure of Y₃N@C₂ₙ (n=40-44) is proposed by the experimental and computational ¹³C NMR studies. The first ⁸⁹Y NMR results for Y₃N@&lt;I&gt;Iₕ&lt;/i&gt;-C₈₀, Y₃N@&lt;I&gt;Cₛ&lt;/i&gt;-C₈₄ and Y₃N@&lt;I&gt;D₃&lt;/i&gt;-C₈₆ reveal a progression from isotropic to restricted (Y₃N)⁶⁺&lt;/sup&gt; cluster motional processes. The di-metallic EMF Y₂C₉₄ is distinguished as a metal-carbide based EMF, Y₂C₂@&lt;I&gt;D₃&lt;/i&gt;-C₉₂. The carbide within the cage is successfully detected by ¹³C NMR. The scalar J&lt;sub&gt;Y-C&lt;/sub&gt; coupling between the yttrium atoms and the C₂ unit within the C₉₂ cage is successfully observed, suggesting the C₂ unit rotates rapidly around the yttrium atoms. Two paramagnetic endohedral metalloheterofullerenes, Y₂@C₇₉N and Gd₂@C₇₉N, were also synthesized and characterized. The EPR study demonstrated that the spin density is mainly localized between the two metallic ions. A spin-site exchange system could be constructed between Y₂@C₇₉N and the organic donor TMPD. Being a unique paramagnetic material, Gd₂@C₇₉N displays an unusual stability over a wide temperature range, which could be very useful in optical and magnetic areas. Functionalization of EMFs is another point of interest in this dissertation. Hydrogenated Sc₃N@C₈₀ was synthesized and characterized. Our study demonstrated that the Sc₃N@C₈₀ can be fully hydrogenated and the pristine Sc₃N@C₈₀ can be recovered from Sc₃N@C₈₀H₈₀ after being heated in vacuum. The hydrogenated EMFs could be potential hydrogen storage materials.","abstract_has_math":false,"creators":["Fu, Wujun"],"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":["Gibson, Harry W.","Heflin, James R.","Ritter, Alfred L.","Morris, John R."],"year":2009,"date_issued":"2009-12-10","date_published":"2009-12-10","updated_at":"2026-07-22T22:19:19Z","subjects":["Metal-carbide","Metalloheterofullerene","Metallofullerene","Hydrogenation","Endohedral","Yttrium-based","Di-metallic"],"languages":["en_US"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-12172009-162249"],"render_values":[{"text":"etd-12172009-162249","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10919/77994","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":["Gibson, Harry W.","Heflin, James R.","Ritter, Alfred L.","Morris, John R."]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Fu, Wujun"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2017-06-09T18:30:45Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2017-06-09T18:30:45Z","2016-09-30"]},{"key":"dc:date.issued","label":"Date","values":["2009-12-10"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Tech"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["Text"]},{"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. 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This dissertation addresses the structural characterization and hydrogenation of EMFs. A family of novel large cage yttrium-based TNT EMFs Y₃N@C₂ₙ (n=40-44) was prepared, separated, and structurally characterized for the first time. The structure of Y₃N@C₂ₙ (n=40-44) is proposed by the experimental and computational ¹³C NMR studies. The first ⁸⁹Y NMR results for Y₃N@<I>Iₕ</i>-C₈₀, Y₃N@<I>Cₛ</i>-C₈₄ and Y₃N@<I>D₃</i>-C₈₆ reveal a progression from isotropic to restricted (Y₃N)⁶⁺</sup> cluster motional processes. The di-metallic EMF Y₂C₉₄ is distinguished as a metal-carbide based EMF, Y₂C₂@<I>D₃</i>-C₉₂. The carbide within the cage is successfully detected by ¹³C NMR. The scalar J<sub>Y-C</sub> coupling between the yttrium atoms and the C₂ unit within the C₉₂ cage is successfully observed, suggesting the C₂ unit rotates rapidly around the yttrium atoms. Two paramagnetic endohedral metalloheterofullerenes, Y₂@C₇₉N and Gd₂@C₇₉N, were also synthesized and characterized. The EPR study demonstrated that the spin density is mainly localized between the two metallic ions. A spin-site exchange system could be constructed between Y₂@C₇₉N and the organic donor TMPD. Being a unique paramagnetic material, Gd₂@C₇₉N displays an unusual stability over a wide temperature range, which could be very useful in optical and magnetic areas. Functionalization of EMFs is another point of interest in this dissertation. Hydrogenated Sc₃N@C₈₀ was synthesized and characterized. Our study demonstrated that the Sc₃N@C₈₀ can be fully hydrogenated and the pristine Sc₃N@C₈₀ can be recovered from Sc₃N@C₈₀H₈₀ after being heated in vacuum. The hydrogenated EMFs could be potential hydrogen storage materials."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D."]},{"key":"dc:title","label":"Title","values":["Preparation, Separation, Characterization and Hydrogenation of Endohedral Metallofullerenes"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Dorn, Harry C."],"dc:contributor.committeemember":["Gibson, Harry W.","Heflin, James R.","Ritter, Alfred L.","Morris, John R."],"dc:contributor.department":["Chemistry"],"dc:creator":["Fu, Wujun"],"dc:date.accessioned":["2017-06-09T18:30:45Z"],"dc:date.available":["2017-06-09T18:30:45Z","2016-09-30"],"dc:date.issued":["2009-12-10"],"dc:description.abstract":["Endohedral metallofullerenes (EMFs) have attracted increasing attention during past decades due to their novel structures and potential applications in a variety of fields such as biomedical applications and molecular electronics. This dissertation addresses the structural characterization and hydrogenation of EMFs. A family of novel large cage yttrium-based TNT EMFs Y₃N@C₂ₙ (n=40-44) was prepared, separated, and structurally characterized for the first time. The structure of Y₃N@C₂ₙ (n=40-44) is proposed by the experimental and computational ¹³C NMR studies. The first ⁸⁹Y NMR results for Y₃N@<I>Iₕ</i>-C₈₀, Y₃N@<I>Cₛ</i>-C₈₄ and Y₃N@<I>D₃</i>-C₈₆ reveal a progression from isotropic to restricted (Y₃N)⁶⁺</sup> cluster motional processes. The di-metallic EMF Y₂C₉₄ is distinguished as a metal-carbide based EMF, Y₂C₂@<I>D₃</i>-C₉₂. The carbide within the cage is successfully detected by ¹³C NMR. The scalar J<sub>Y-C</sub> coupling between the yttrium atoms and the C₂ unit within the C₉₂ cage is successfully observed, suggesting the C₂ unit rotates rapidly around the yttrium atoms. Two paramagnetic endohedral metalloheterofullerenes, Y₂@C₇₉N and Gd₂@C₇₉N, were also synthesized and characterized. The EPR study demonstrated that the spin density is mainly localized between the two metallic ions. A spin-site exchange system could be constructed between Y₂@C₇₉N and the organic donor TMPD. Being a unique paramagnetic material, Gd₂@C₇₉N displays an unusual stability over a wide temperature range, which could be very useful in optical and magnetic areas. Functionalization of EMFs is another point of interest in this dissertation. Hydrogenated Sc₃N@C₈₀ was synthesized and characterized. Our study demonstrated that the Sc₃N@C₈₀ can be fully hydrogenated and the pristine Sc₃N@C₈₀ can be recovered from Sc₃N@C₈₀H₈₀ after being heated in vacuum. The hydrogenated EMFs could be potential hydrogen storage materials."],"dc:description.degree":["Ph. D."],"dc:identifier.other":["etd-12172009-162249"],"dc:identifier.uri":["http://hdl.handle.net/10919/77994"],"dc:language.iso":["en_US"],"dc:publisher":["Virginia Tech"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:subject":["Metal-carbide","Metalloheterofullerene","Metallofullerene","Hydrogenation","Endohedral","Yttrium-based","Di-metallic"],"dc:title":["Preparation, Separation, Characterization and Hydrogenation of Endohedral Metallofullerenes"],"dc:type":["Dissertation"],"dc:type.dcmitype":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Ph. D."],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:19:19Z"}