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Exohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenes

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Exohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenes Exohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenes Erick Barton Iezzi Dissertation submitted to the Faculty of Virginia Polytechnic Institute and State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Harry C. Dorn, Chair James M. Tanko Brian E. Hanson Paul A. Deck Timothy E. Long October 14, 2003 Blacksburg, Virginia Keywords: Metallofullerene, endohedral, functionalization, X-ray contrast, scandium nitride Copyright 2003, Erick B. Iezzi Exohedral Functionalization and Applications of the Trimetallic Nitride Endohedral Metallofullerenes Erick B. Iezzi (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 (D5h) of Sc3N@C80, the synthesis of Lu3N@C80 as a 15 15 novel X-ray contrasting agent, and the synthesis of Sc3 N@C80 with N2 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 15 dibenzyl malonate adducts of Sc3N@C80 were synthesized, in addition to a N-labeled terminal amine derivative. Water-soluble metallofullerenols, Sc3N@C80(OH)~10(O)~10, were synthesized from polyanionic intermediates. 13 The Sc3N@C78 metallofullerene was derivatized with a C-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 D5h symmetry, as indicated by the time- averaged six line 13C NMR spectrum with a 1:2:2:1:1:1 ratio. 15 The internal metal-nitride cluster of Sc3N@C80 was synthesized with a N-label for studying the motion(s) of the cluster (within the carbon cage) at various temperatures using 15N NMR spectroscopy. Acknowledgements I would like to thank my Ph.D. advisor, Dr. Harry C. Dorn, for his guidance, friendship and support during my tenure as a graduate student at Virginia Tech. We met under the most unusual of circumstances (during lunch at Burger King), and I am grateful that he accepted me as a student when I was contemplating leaving Virginia Tech. I thank him for allowing me to develop a project that has enabled me to achieve publications and accolades that I never thought possible. Furthermore, I thank him for his empathy during the periods when I was extremely frustrated with my project and/or the lack of starting materials. I am glad we were able to accomplish all the goals of the project, and I hope that metallofullerene research grants him luck and prosperity. There are several faculty members in the chemistry department that I would like to acknowledge. First of all, I thank the members of my Ph.D. committee (Dr. James Tanko, Dr. Paul Deck, Dr. Brian Hanson and Dr. Tim Long) for the help and guidance they gave over the past four years. I especially thank Dr. Tanko for his guidance with departmental policies (i.e., literature review) when there seemed to be a lack of structure in the graduate curriculum, along with the several letters of recommendation that he was kind enough to write for me over the last two years. I thank Dr. Paul Carlier for a letter of recommendation and for helping with the essay that facilitated me winning an ACS Division of Organic Chemistry Graduate Fellowship. I thank Dr. Richard Gandour for his guidance and help with the proposal section of the NIH postdoctoral fellowship that I hope to win, and I thank him for writing a letter of recommendation. In addition, I thank Dr. Alan Esker for all his helpful advice, for writing a letter of recommendation for the ACS fellowship, and for giving me a place to live during the final months of my graduate career. I would like to thank Tom Glass in Analytical Services for help with running numerous NMR samples. Without Tom, several portions of my Ph.D. project would not have been successful. I also thank my colleague, Dr. James Duchamp (Emory and Henry College), for all his work and helpful discussions over the past few years. Jim was a great friend and basically my only lab mate at Virginia Tech. Finally, and most importantly, I would like to thank both God and my parents. I thank God for answering my prayers and helping me through the tough times, and I hope that I am continually blessed with good fortune throughout my life. As for my parents, I could not have achieved this degree without them. They were always there for me when I needed them, and they are the most loving and caring parents that a son could have. iii Table of Contents Page CHAPTER 1 − Introduction and Background……………………..……..…..……….1 1.1. Historical overview…………………………………………………………..……1 1.1.1. C60 and empty-cage fullerenes……….………………………………….…...1 1.1.2. Endohedral metallofullerenes……………………………………….……….2 1.1.2.1. Traditional metallofullerenes………………………………….………..2 1.1.2.2. Trimetallic nitride endohedral metallofullerenes…………….…………3 1.2. Synthesis, isolation, purification and mechanistic formation………….………….6 1.2.1. Synthesis of fullerenes and metallofullerenes……………………..…………6 1.2.2. Extraction from soot……………………………………………….………...8 1.2.3. Purification by liquid chromatography…………………………….………...9 1.2.4. Mechanistic formation of fullerenes and metallofullerenes……….………..11 1.3. Structure and cage stability…………………………………………….………...12 1.3.1. Isolated-pentagon rule (IPR)…………………………………….………….12 1.3.2. Icosahedral symmetry and charge transfer…………………………………13 1.3.3. Internal motion and electrostatic potential………………………….………16 1.4. Organic functionalization of C60 and traditional metallofullerenes……….……..18 1.4.1. Reactivity of the C60 fullerene……………………………………………...18 1.4.1.1. Hydroxylation of C60 ...……………………………………….….……19 1.4.1.2. C60 anions and the addition of nucleophiles…………………………..20 1.4.1.3. Cycloaddition reactions with C60 ...…………………………………...24 1.4.1.4. Radical additions to C60 ...…………………………………………….26 1.4.2. Reactivity of traditional metallofullerenes………………………………….28 1.4.2.1. Radical addition with traditional metallofullerenes…………………...28 1.4.2.2. Electrophilic and nucleophilic additions………………………………30 1.4.2.3. Hydroxylation of traditional metallofullerenes………………………..30 1.5. Electronic properties of traditional and trimetallic nitride metallofullerenes……31 1.5.1. Electrochemistry……………………………………………………………31 1.5.2. UV-Vis-NIR absorption…………………………………………………….32 1.6. Fullerene and metallofullerene-based materials…………………………………33 1.6.1. Fullerene-containing polymers……………………………………………..33 1.6.2. Films, mono-layers, supramolecular assemblies and nanodevices…………38 1.6.3. Medicinal applications of fullerenes and metallofullerenes………………..42 1.6.3.1. Medicinal applications with C60 fullerene…………………………….42 1.6.3.1.1. Toxicity studies…………………………………………………..42 1.6.3.1.2. Antiviral activity…………………………………………………43 1.6.3.1.3. Neuroprotective ability…………………………………………..45 1.6.3.2. Medicinal applications of metallofullerenes…………………………..45 1.6.3.2.1. MRI contrast agents and biodistribution…………………………45 1.6.3.3. Radiopharmaceuticals and biodistribution…………………………….48 CHAPTER 2 − Project Overview………………...……………………………………50 iv CHAPTER 3 − Functionalization of Sc3N@C80 …………………..……………….....53 3.1. Introduction……………………………………………………………………....53 3.2. Results and Discussion…………………………………………………………..55 3.2.1. The first derivative of Sc3N@C80 ………………………………….………55 3.2.2. X-ray crystal structure of the first Sc3N@C80 derivative………………..….62 3.2.3. Malonate derivatives of Sc3N@C80 ………………………………………..65 15 3.2.4. A N-labeled terminal amine derivative of Sc3N@C80 for addend attachment……………………………………………………….....68 3.2.4.1. 1,3-Dihydrobenzo[c]thiophene (10)……….…………………………..69 3.2.4.2. 1,3-Dihydrobenzo[c]thiophene-2,2-dioxide (11)……………………...71 3.2.4.3. 1,3-Dihydro-5-nitrobenzo[c]thiophene-2,2-dioxide (15N-labeled) (12)……………………………………………………...71 3.2.4.4. 5-Amino-1,3-dihydrobenzo[c]thiophene-2,2-dioxide (15N-labeled) (13)……………………………………………………...73 15 3.2.4.5. Terminal amine derivative of Sc3N@C80 ( N-labeled) (14)……….....74 3.2.5. Water-soluble metallofullerenols from Sc3N@C80 (15)……………………76 3.3. Experimental……………………………………………………………………..81 3.3.1. Materials and purification…………………………………………………..81 3.3.2. Analytical methods…………………………………………………………82 3.3.3. Synthesis of 13C-labeled 6,7-dimethoxyisochroman-3-one (2)…………….84 13 3.3.4. Synthesis of C-labeled Sc3N@C80–C10H12O2 cycloadduct (4)…………...87 13 3.3.5. Synthesis of C-labeled diethyl malonate adduct of Sc3N@C80 (6)……….95 3.3.6. Synthesis of dibenzyl malonate adduct of Sc3N@C80 (8).………………….97 3.3.7. Synthesis of 1,3-dihydrobenzo[c]thiophene (10)…………………………...99 3.3.8. Synthesis of 1,3-dihydrobenzo[c]thiophene-2,2-dioxide (11)…………….102 3.3.9. Synthesis of 15N-labeled 1,3-dihydro-5-nitrobenzo[c]thiophene- 2,2-dioxide (12)……………………………………………………………105 3.3.10. Synthesis of 15N-labeled 5-amino-1,3-dihydrobenzo[c]thiophene- 2,2-dioxide (13)…………………………………………………………..108 15 3.3.11.
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