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Chapter 3 Functionalization of C70: Water Research Collection Doctoral Thesis Synthesis and Characterization of Fullerene and Metallofullerene Derivatives by Prato Reaction Author(s): Tiu, Elisha Gabrielle V. Publication Date: 2017 Permanent Link: https://doi.org/10.3929/ethz-b-000228807 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library Diss. ETH NO. 24504 Synthesis and Characterization of Fullerene and Metallofullerene Derivatives by Prato Reaction A thesis submitted to attain the degree of DOCTOR OF SCIENCES of ETH Zurich (Dr. Sc. ETH Zurich) presented by Elisha Gabrielle V. Tiu Master of Science in Chemistry, Osaka University, Osaka, Japan born January 22nd 1990 citizen of Philippines accepted on the recommendation of Prof. Dr. Yoko Yamakoshi, examiner Prof. Dr. Carlo Thilgen, co-examiner 2017 Acknowledgements I would like to express my gratitude towards the people who supported me throughout my study: First of all, I would like to thank Prof. Dr. Yoko Yamakoshi for giving me the opportunity to work in ETH Zurich. I truly appreciate her guidance and help in refining me to become the person that I am today. I am deeply indebted to her for the training she gave me; she always had my best interest in mind, especially for my future career. I really thank her for all the things I have learned during my stay in her laboratory. Although challenging, I was truly interested in the projects I worked on, and I learned a lot. I would like to thank Prof. Dr. Carlo Thilgen for being the co-examiner of my thesis. During my study, he was always available to discuss with. He was always willing to help me in however way he can and I really appreciated that. I would also like to thank Prof. Dr. François Diederich and Prof. Dr. Jeffrey Bode for allowing me to attend their group meetings and for letting me to use their group equipment. I also appreciated the good friendships I formed with the members of their groups. I also extend my gratitude to Prof. Dr. Massimo Morbidelli for providing access to the DLS machine and to Prof. Lucio Isa for providing access to the tensiometer. Furthermore, I would like to thank to our group members: Sean Oriana, Safwan Aroua, Rakesh Kumar, Masayuki Nasuda, Alessandro Fracassi, Dac Ngan Nguyen-Giang, Ankita Ray, Korinne Liosi, Gabriele Zirpoli for the fun, laughter, and memorable times we enjoyed together. I would also like to thank my collaborators Dr. Silvia Osuna and Dr. Marc Garcia-Borràs for the meaningful discussions and the work we have done together. I would also like to thank Dr. Alla Sologubenko from ScopeM for taking extra time to help me in my STEM measurements. I also appreciate the help of Dr. Takashi Ishikawa for his expertise in cryoTEM, for his insights and discussions with him. i I would like to especially thank NMR services, particularly, Mr. René Arnold, for all his efficiency and patience in measuring my samples in the smallest quantities and sensitive conditions. I would also like to extend my gratitude to Mr. Stephan Burkhardt and Mr. Rainer Frankenstein for their extensive support. I would like to specially thank Mass services group, in particular Dr. Xiangyang Zhang, for his advice and his mentoring when I had problems in my mass spectra. He was very efficient in measuring my samples. I also would like to thank the crystallographers, in particular Dr. Nils Trapp and Mr. Michael Solar for their efforts in measuring many of my crystal samples. They provided me with many meaningful advices. I also would like to thank Mr. Mario Kessinger and Ms. Helen Kaufmann-Baumgartner for their administrative help. They were very efficient and helpful. Finally, I would like to thank my grandmother for the inspiration she gave me to finish the race. Her strength, wisdom, and courage will always and forever be an inspiration for me. I would like to thank my friends, my relatives, my sister, my father, my mother, and my husband for the unwavering support they showered me throughout the years I spent abroad for my higher education. They were always there during the most difficult times. Truly, there is no distance that can separate us. ii List of Publications and Presentations Publications 1. E.G.V. Tiu, K. Liosi, S. Aroua, Y. Yamakoshi, J. Mater. Chem. B 2017, 5, 6676 – 6680. Micelle vs Vesicle Formation Controlled by Distal Functionalization of C60-PEG Conjugates. 2. S. Aroua, E.G.V. Tiu, T. Ishikawa, Y. Yamakoshi, Helv. Chim. Acta 2016, 99, 805 – 813. Well-Defined Amphiphilic C60-PEG Conjugates: Water-Soluble and Thermoresponsive Materials. 3. R. Kumar, E. Gleißner, E.G.V. Tiu, and Y. Yamakoshi, Org. Lett., 2016, 18, 184 – 187. C70 as a Photocatalyst for Oxidation of Secondary Benzylamines to Imines. 4. S. Aroua, E.G.V. Tiu, M. Ayer, T. Ishikawa, Y. Yamakoshi Polym. Chem. 2015, 6, 2616. RAFT Synthesis of Poly(vinylpyrrolidone) Amine and Preparation of a Water-Soluble C60-PVP Conjugate. Oral Presentation E.G.V. Tiu, S. Aroua, and Y. Yamakoshi “Synthesis of a Well-Defined, Water- th Soluble C60-PVP Conjugate,” The 229 Electrochemical Society Meeting. San Diego, California, USA (2016). Poster Presentations • E.G.V. Tiu, S. Aroua, T. Ishikawa, and Y. Yamakoshi “Synthesis of a Well-Defined, Water-Soluble C60-PVP Polymer: a Potential PDT Agent,” The 8th Symposium SSCI Scholarship Fund of the Swiss Chemical Industry. Zurich, Switzerland (2016). • E.G.V. Tiu, S. Aroua, T. Ishikawa, and Y. Yamakoshi “Synthesis of a Well-Defined, Water-Soluble C60-PVP Polymer: a Potential PDT Agent,” The 16th International Symposium on Novel Aromatic Compounds. Madrid, Spain (2015). iii iv Table of Contents List of Common Terms and Abbreviations ....................................................... ix Abstract .......................................................................................................... xiii Résumé ......................................................................................................... xvii Chapter 1: General Introduction ....................................................................... 1 1.1 Fullerenes: Discovery and Production ....................................................... 3 1.2 The Structures of Fullerenes ...................................................................... 4 1.2.1 C60 Fullerene ....................................................................................... 5 1.2.2 C70 Fullerene ....................................................................................... 6 1.2.3 Metallofullerenes ................................................................................. 7 1.3 The Properties of Fullerenes ...................................................................... 8 1.3.1 C60 Fullerene ....................................................................................... 8 1.3.2 C70 Fullerene ..................................................................................... 10 1.3.3 Metallofullerenes ............................................................................... 11 1.3.3.1 Electronic Properties ................................................................... 11 1.3.3.2 Metal Cluster Dynamics .............................................................. 12 1.3.3.3 Geometry of the Metal Cluster .................................................... 13 1.4 Purification of Fullerenes ......................................................................... 14 1.5 Chemical Reactions of Fullerenes ........................................................... 16 1.5.1 Reduction Reactions ......................................................................... 16 1.5.2 Oxidation Reactions .......................................................................... 16 1.5.3 Halogenations ................................................................................... 17 1.5.4 Radical Reaction ............................................................................... 18 1.5.5 Nucleophilic Additions ....................................................................... 18 1.5.6 Cyclopropanation: The Bingel-Hirsch Addition .................................. 20 1.5.7 Cycloaddition Reactions .................................................................... 20 1.5.7.1 [1+2] Cycloaddition ..................................................................... 21 1.5.7.2 [2+2] Cycloaddition ..................................................................... 23 1.5.7.3 [4+2] Cycloaddition: Diels-Alder reaction .................................... 26 1.5.7.4 [3+2] Cycloaddition ..................................................................... 27 1.5.7.4.1 Prato Reaction (1,3-Dipolar Cycloaddition of Azomethine Ylides) on C60 and C70 ............................................................................ 28 1.5.7.4.2 Mono-functionalization on M3N@C80 by Prato reaction ....... 29 1.5.7.4.3 Prato Bis-functionalization on M3N@C80 ............................. 30 1.6 Applications of Fullerenes ........................................................................ 31 1.6.1 Organic Photovoltaics ....................................................................... 31 1.6.2 Hydrogen Gas Storage ...................................................................... 32 1.6.3 Fullerenes as Biological Materials ..................................................... 33 1.6.3.1 Photodynamic Therapy ............................................................... 33 1.6.3.2 MRI Contrast
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