An Overview of Fullerene Chemistry
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Deoxygenation Supplemental Without Spectra
Novel Organic Transformations Arising from Gold(I) Chemistry By Mathieu André Morin Thesis submitted to the faculty of Graduate and Postdoctoral Studies In partial fulfillment of the requirements for the Ph.D. degree in chemistry Candidate Supervisor Mathieu André Morin Dr. Louis Barriault Ottawa-Carleton Chemistry Institute Faculty of Science University of Ottawa © Mathieu André Morin, Ottawa, Canada, 2017 Abstract The use of gold in organic chemistry is a relatively recent occurrence. In addition to being previously considered too expensive, it was also believed to be chemically inert. Soon after the early reports indicating its rich reactivity, the number of reports on chemical transformations involving gold sky rocketed. One such report by Toste and coworkers demonstrated the intramolecular addition of silyl enol ether onto Au(I) activated alkynes, resulting in a 5-exo dig cyclization. The first part (Chapter 1) of this thesis discusses the development of a Au(I) catalyzed polycyclization reaction inspired by this transformation. The reaction demonstrated the ability of Au(I) to successfully catalyze the formation of multiple C-C bonds and resulted in the synthesis of benzothiophenes, benzofurans, carbazoles and hydrindene. With the current resurgence of photochemical transformations being reported in literature, various opportunities for the use of Au(I) complexes arose. The substantial relativistic effect observed in gold which make it a good soft Lewis acid also has a significant influence on the redox potential of this metal. Chapter 3 of this thesis discusses the development of a Au(I) photocatalyzed process which benefits from having both a strong oxidation and reduction potential for the reduction of carbon-halide bonds. -
Chapter 1 Tropone and Tropolone
School of Molecular and Life Sciences New Routes to Troponoid Natural Products Jason Matthew Wells This thesis is presented for the Degree of Doctor of Philosophy of Curtin University November 2018 Declaration To the best of my knowledge and belief this thesis contains no material previously pub- lished by any other person except where due acknowledgement has been made. This thesis contains no material which has been accepted for the award of any other degree or diploma in any other university. Signature: Date: i Abstract Malaria is an infectious disease found in humans and other animals, it is caused by a single-cell parasite of the Plasmodium genus with many different substrains. Of these, P. falciparum is the most deadly to humans causing the majority of deaths. Although research into the area of antimalarial compounds is wide spread, few have been devel- oped with new structural features. Cordytropolone 37 is a natural product isolated in 2001 from the insect pathogenic fungus Cordyceps sp. BCC 1681 and has been shown to have antimalarial activity against P. falciparum. It has a structure unrelated to antimalarial com- pounds currently used in therapy. It does not contain a peroxide bridge as with artemisinin 25 or quinoline rings as with chloroquine 22. This unique structure indicates that it could possibly interact with the malaria parasite in a fashion unlike current treatments. In order for cordytropolone to be further developed as a potential treatment, it must first be synthe- sised in a laboratory environment. This study attempts to develop the first total synthesis of cordytropolone. H HO O N O O N O N H H H O O Cl HO O 22 25 37 Figure 0.0.1: Cordytropolone 37 has a unique structure compared to the current common malaria treatments The first method investigated towards the total synthesis of cordytropolone involved an intramolecular Buchner ring expansion. -
A Post-Buckminsterfullerene View of Carbon Chemistry
A POST-BUCKMINSTERFULLERENE VIEW OF CARBON CHEMISTRY Harold Kroto School of Chemistry and Molecular Sciences, University of Sussex, Brighton, BNI 9QJ UK Keywords: Cs0, Fullerenes, carbon particles INTRODUCTION The discovery of c60 Buckminsterfullerene, Fig 1, has its origins in a research programme involving synthetic chemistry, microwave spectroscopy and radioastronomyl. In 1915, at Sussex (with David Walton), the long chain polyyne H-CeC-CsC-CsN was synthesised and studied by microwave spectroscopy. Subsequently, with Takeshi Oka and NRC(0ttawa) astronomers, the molecule was discovered in space, Fig 2, by radioastronomy using the laboratory microwave frequencies. This discovery led on to the detection of the even longer carbon chain molecules HCTN, HCgN and HCl.lN in the space between the stars2. Further work aimed at understanding the formation of the chains in space focussed attention on the possibility that they are produced at the same time as carbon dust in red giant stars1,*. During experiments at Rice University in 1985 (with James Heath, Sean O'Brien, Robert Curl and Richard Smalley), designed to simulate the conditions in these stars and explore their capacity for carbon chain formation, the exciting discovery that C60 was remarkably stable was made3. It was found that under conditions where almost all the atoms in a carbon plasma had nucleated to form microparticles the molecule c60 remained behind - together with some CTO. This result was, as is now well 'known, rationalised on the basis of the closed cage structure shown in Fig 1. It was proposed that the geodesic and aromatic factors inherent in such a structure could account for the stability of the molecule. -
Metallofullerene and Fullerene Formation from Condensing Carbon Gas Under Conditions of Stellar Outflows and Implication to Star
Metallofullerene and fullerene formation from condensing carbon gas under conditions of stellar outflows and implication to stardust Paul W. Dunka,b,1, Jean-Joseph Adjizianc, Nathan K. Kaiserb, John P. Quinnb, Gregory T. Blakneyb, Christopher P. Ewelsc,1, Alan G. Marshalla,b,1, and Harold W. Krotoa,1 aDepartment of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306; bIon Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310; and cInstitut des Matériaux Jean Rouxel, Centre National de la Recherche Scientifique, Unité Mixte de Recherche 6502, Université de Nantes, BP 32229 Nantes, France Contributed by Harold W. Kroto, August 29, 2013 (sent for review June 13, 2013) Carbonaceous presolar grains of supernovae origin have long confirmed to exist in circumstellar and interstellar environments. been isolated and are determined to be the carrier of anomalous C60 and C70 were first unequivocally detected in a planetary 22Ne in ancient meteorites. That exotic 22Ne is, in fact, the decay nebula in 2010, which was thought to be hydrogen deficient (11). isotope of relatively short-lived 22Na formed by explosive nucleo- Thereafter, Buckminsterfullerene was detected in hydrogen- synthesis, and therefore, a selective and rapid Na physical trapping rich [including the least H-deficient R Coronae Borealis stars] mechanism must take place during carbon condensation in super- (12, 13) and oxygen-rich environments (14), as well as the ISM nova ejecta. Elucidation of the processes that trap Na and produce (15) and a protoplanetary nebula (16). Moreover, fullerenes large carbon molecules should yield insight into carbon stardust have been detected in a host of other circumstellar and in- enrichment and formation. -
Carbon Nanostructures – from Molecules to Functionalised Materials
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 1537 Carbon Nanostructures – from Molecules to Functionalised Materials Fullerene-Ferrocene Oligomers, Graphene Modification and Deposition MICHAEL NORDLUND ACTA UNIVERSITATIS UPSALIENSIS ISSN 1651-6214 ISBN 978-91-513-0019-1 UPPSALA urn:nbn:se:uu:diva-327189 2017 Dissertation presented at Uppsala University to be publicly examined in A1:107a, BMC, Husargatan 3, Uppsala, Friday, 22 September 2017 at 09:15 for the degree of Doctor of Philosophy. The examination will be conducted in English. Faculty examiner: Professor Mogens Brøndsted Nielsen (Copenhagen University, Department of chemistry). Abstract Nordlund, M. 2017. Carbon Nanostructures – from Molecules to Functionalised Materials. Fullerene-Ferrocene Oligomers, Graphene Modification and Deposition. Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 1537. 64 pp. Uppsala: Acta Universitatis Upsaliensis. ISBN 978-91-513-0019-1. The work described in this thesis concerns development, synthesis and characterisation of new molecular compounds and materials based on the carbon allotropes fullerene (C60) and graphene. A stepwise strategy to a symmetric ferrocene-linked dumbbell of fulleropyrrolidines was developed. The versatility of this approach was demonstrated in the synthesis of a non- symmetric fulleropyrrolidine-ferrocene-tryptophan triad. A new tethered bis-aldehyde, capable of regiospecific bis-pyrrolidination of a C60-fullerene in predominantly trans fashion, was designed, synthesised and reacted with glycine and C60 to yield the desired N-unfunctionalised bis(pyrrolidine)fullerene. A catenane dimer composed of two bis(pyrrolidine)fullerenes was obtained as a minor co-product. From the synthesis of the N-methyl analogue, the catenane dimer could be separated from the monomeric main product and fully characterised by NMR spectroscopy. -
Formation of Buckminsterfullerene (C60) in Interstellar Space
Formation of buckminsterfullerene ( ) C60 in interstellar space Olivier Berné1 and A. G. G. M. Tielens Leiden Observatory, Leiden University, P.O. Box 9513, NL- 2300 RA Leiden, The Netherlands Edited by Neta A. Bahcall, Princeton University, Princeton, NJ, and approved November 2, 2011 (received for review August 31, 2011) Buckminsterfullerene (C60) was recently confirmed as the largest region, at high angular resolution (Fig. 1). This measurement can molecule identified in space. However, it remains unclear how be used to derive the integrated intensity radiated by the nebula, and where this molecule is formed. It is generally believed that which can be used as a calibrator, to convert the Spitzer observa- C60 is formed from the buildup of small carbonaceous compounds tions of the PAHs and C60 bands into absolute chemical abun- in the hot and dense envelopes of evolved stars. Analyzing infrared dances of these species, allowing a quantitive study of PAH and observations, obtained by Spitzer and Herschel, we found that C60 C60 chemical evolution. is efficiently formed in the tenuous and cold environment of an interstellar cloud illuminated by strong ultraviolet (UV) radiation Measurement of the Far Infrared Integrated Intensity of Dust Emission I fields. This implies that another formation pathway, efficient at in the Nebula. The far infrared integrated intensity FIR was ex- low densities, must exist. Based on recent laboratory and theore- tracted by fitting the spectral energy distribution (SED) at each tical studies, we argue that polycyclic aromatic hydrocarbons are position in the cross-cut shown in Fig. 1. For these positions, we converted into graphene, and subsequently C60, under UV irradia- have used the brightnesses as measured by Herschel Photodetec- tion from massive stars. -
Reactions of Graphene Oxide and Buckminsterfullerene in the Aquatic Environment Yingcan Zhao Purdue University
Purdue University Purdue e-Pubs Open Access Dissertations Theses and Dissertations 8-2016 Reactions of graphene oxide and buckminsterfullerene in the aquatic environment Yingcan Zhao Purdue University Follow this and additional works at: https://docs.lib.purdue.edu/open_access_dissertations Part of the Environmental Engineering Commons Recommended Citation Zhao, Yingcan, "Reactions of graphene oxide and buckminsterfullerene in the aquatic environment" (2016). Open Access Dissertations. 896. https://docs.lib.purdue.edu/open_access_dissertations/896 This document has been made available through Purdue e-Pubs, a service of the Purdue University Libraries. Please contact [email protected] for additional information. Graduate School Form 30 Updated PURDUE UNIVERSITY GRADUATE SCHOOL Thesis/Dissertation Acceptance This is to certify that the thesis/dissertation prepared By Yingcan Zhao Entitled REACTIONS OF GRAPHENE OXIDE AND BUCKMINSTERFULLERENE IN THE AQUATIC ENVIRONMENT For the degree of Doctor of Philosophy Is approved by the final examining committee: Chad T. Jafvert Chair Timothy R. Filley Inez Hua Ronald F. Turco To the best of my knowledge and as understood by the student in the Thesis/Dissertation Agreement, Publication Delay, and Certification Disclaimer (Graduate School Form 32), this thesis/dissertation adheres to the provisions of Purdue University’s “Policy of Integrity in Research” and the use of copyright material. Approved by Major Professor(s): Chad T. Jafvert Approved by: Dulcy M. Abraham 6/21/2016 Head of the Departmental Graduate Program Date i REACTIONS OF GRAPHENE OXIDE AND BUCKMINSTERFULLERENE IN THE AQUATIC ENVIRONMENT A Dissertation Submitted to the Faculty of Purdue University by Yingcan Zhao In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy August 2016 Purdue University West Lafayette, Indiana ii To my parents and Liang, for their love, support and encouragement. -
Diels -Alder Reactions Between Fullerene[60] and Various Pentacenes
University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Winter 2000 Diels -Alder reactions between fullerene[60] and various pentacenes James Mack II. University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Mack, James II., "Diels -Alder reactions between fullerene[60] and various pentacenes" (2000). Doctoral Dissertations. 2147. https://scholars.unh.edu/dissertation/2147 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy subm itted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. -
Synthesis of Novel Fullerene Architectures with Mixed Octahedral Addition Pattern Synthese Neuartiger Fulleren Architekturen
Synthesis of Novel Fullerene Architectures with Mixed Octahedral Addition Pattern Synthese neuartiger Fulleren Architekturen mit gemischtem oktaedrischen Additionsmuster Der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr. rer. nat. vorgelegt von Ekaterini Vlassiadi aus Nürnberg Als Dissertation genehmigt von der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 24.07.2017 Vorsitzender der Promotionskommission: Prof. Dr. Georg Kreimer Gutachter: Prof. Dr. Andreas Hirsch Prof. Dr. Jürgen Schatz Mein besonderer Dank gilt meinem Doktorvater Prof. Dr. Andreas Hirsch für die Bereitstellung des interessanten und herausfordernden Themas, seine Förderung, die fachliche Unterstützung und das Interesse am Fortgang meiner Forschungsarbeit. Die vorliegende Arbeit entstand in der Zeit von November 2012 bis Dezember 2016 am Lehrstuhl für Organische Chemie II des Departments für Chemie und Pharmazie der Friedrich-Alexander-Universität Erlangen-Nürnberg. Table of Contents 1. Introduction 1 1.1. Discovery of Fullerenes 1 1.2. Structure of C60 2 1.3. Physical and Spectroscopic Properties of C60 3 1.3.1. Solubility 3 1.3.2. Mass Spectrometry 4 1.3.3. NMR Spectroscopy 4 1.3.4. UV/Vis Spectroscopy 6 1.4. Electronic Properties and Chemical Reactivity of [60] Fullerene 7 1.5. Chemical reactivity of Fullerenes 10 1.5.1. Endohedral Functionalization of C60 10 1.5.2. Fulleride Salts 11 1.5.3. Heterofullerenes 12 1.5.4. Open-Shell Fullerene Fragments 12 1.5.5. Exohedral Functionalization of C60 13 1.5.5.1 Addition of Nucleophiles 13 1.5.5.2. Cycloaddition reactions 15 1.6. Multiple Exohedral Functionalization 18 1.6.1 Introduction to the Nomenclature of Multiple-Adducts 18 1.6.2. -
Carbon-Based Nanomaterials/Allotropes: a Glimpse of Their Synthesis, Properties and Some Applications
materials Review Carbon-Based Nanomaterials/Allotropes: A Glimpse of Their Synthesis, Properties and Some Applications Salisu Nasir 1,2,* ID , Mohd Zobir Hussein 1,* ID , Zulkarnain Zainal 3 and Nor Azah Yusof 3 1 Materials Synthesis and Characterization Laboratory (MSCL), Institute of Advanced Technology (ITMA), Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia 2 Department of Chemistry, Faculty of Science, Federal University Dutse, 7156 Dutse, Jigawa State, Nigeria 3 Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia; [email protected] (Z.Z.); [email protected] (N.A.Y.) * Correspondence: [email protected] (S.N.); [email protected] (M.Z.H.); Tel.: +60-1-2343-3858 (M.Z.H.) Received: 19 November 2017; Accepted: 3 January 2018; Published: 13 February 2018 Abstract: Carbon in its single entity and various forms has been used in technology and human life for many centuries. Since prehistoric times, carbon-based materials such as graphite, charcoal and carbon black have been used as writing and drawing materials. In the past two and a half decades or so, conjugated carbon nanomaterials, especially carbon nanotubes, fullerenes, activated carbon and graphite have been used as energy materials due to their exclusive properties. Due to their outstanding chemical, mechanical, electrical and thermal properties, carbon nanostructures have recently found application in many diverse areas; including drug delivery, electronics, composite materials, sensors, field emission devices, energy storage and conversion, etc. Following the global energy outlook, it is forecasted that the world energy demand will double by 2050. This calls for a new and efficient means to double the energy supply in order to meet the challenges that forge ahead. -
Molecular Vibrational Modes of C60 and C70 Via Finite Element Method
European Journal of Mechanics A/Solids 28 (2009) 948–954 Contents lists available at ScienceDirect European Journal of Mechanics A/Solids journal homepage: www.elsevier.com/locate/ejmsol Molecular vibrational modes of C60 and C70 via finite element method Du Jing a,b, Zeng Pan a,b,* a Department of Mechanical Engineering, Tsinghua University, Beijing 100084, China b Key Laboratory for Advanced Materials Processing Technology, Ministry of Education of China, China article info abstract Article history: Molecular vibration spectra are of great significance in the study of molecular structures and characters. Received 26 September 2006 A widely-used analytical method of structural mechanics, finite element method, is imported into the Accepted 17 February 2009 domain of micro-scaled molecular spectra. The vibrational modes of fullerenes C60 and C70 are calculated Available online 28 February 2009 depending on uniform carbon–carbon bonding elements, each of which has three force constants that are determined by fitting the C60 Raman spectra experimental data and one ratio factor which is the Keywords: bond lengths ratio between the single and double bonds. The computational result shows reasonable Finite element method agreement with both calculated and experimental results published before. Fullerene Ó 2009 Published by Elsevier Masson SAS. C70 Molecular spectra 1. Introduction overlap (MNDO) (Stanton and Newton, 1988), Quantum-mechan- ical Consistent Force Field Method for Pi-Electron Systems (QCFF/ Since Kroto et al. discovered C60 by laser vaporizing graphite PI) (Negri et al., 1988), Austin Model 1 (AM1) (Slanina et al., 1989), into a helium stream (Kroto et al., 1985); an impressive experi- density functional theory (Adams et al., 1991; Choi et al., 2000; mental and theoretical effort has been undertaken towards this Schettino et al., 2001; Sun and Kertesz, 2002; Schettino et al., 2002). -
Fluorinated Butatrienes
Fluorinated Butatrienes Dissertation zur Erlangung des akademischen Grades des Doktors der Naturwissenschaften (Dr. rer. nat.) eingereicht im Fachbereich Biologie, Chemie, Pharmazie der Freien Universität Berlin vorgelegt von Dipl.-Chem. Christian Ehm aus Berlin Berlin, April 2010 1. Gutachter: Prof. Dr. Dieter Lentz 2. Gutachter: Prof. Dr. Beate Paulus Disputation am 28.6.2010 I Acknowledgements It would not have been possible to write this doctoral thesis without the help and support of the kind people around me, to only some of whom it is possible to give particular mention here. First and foremost I would like to thank my principal supervisor, Professor Dieter Lentz, for the opportunity of doing research in his group. Without his continuous support and encouragement this thesis would not be in the present state. I highly appreciate that Professor Beate Paulus has agreed to be co-referee of my thesis. I would like to cordially thank Lada for her love and patience as well as her interest in my research. Special thanks to my family for their continuous support and love. I would like to thank Mike Roland, Sten Dathe and Sven Wünsche for their friendship and the fun we have had every Sunday evening. Special thanks to Sebastian Freitag, Boris Bolsinger and Frederic Heinrich for their friendship. They deserve much gratefulness for keeping me on the right way. I would like to thank all my colleagues at the Institut für Chemie und Biochemie, Abteilung Anorganische Chemie. In particular I want to thank all members of the Lentz group, Thomas Hügle, Moritz Kühnel, Dr. Floris Akkerman, Dr.