Endohedral Fullerenes: Synthesis, Isolation, Mono- and Bis-Functionalization ⇑ ⇑ Maira R
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Photoionization of the Cerium Isonuclear Sequence and Cerium Endohedral Fullerene
University of Nevada, Reno Photoionization of the Cerium Isonuclear Sequence and Cerium Endohedral Fullerene A dissertation submitted in partial ful¯llment of the requirements for the degree of Doctor of Philosophy in Physics by Mustapha Habibi Prof. Ronald A. Phaneuf/Dissertation Advisor May, 2009 THE GRADUATE SCHOOL We recommend that the dissertation prepared under our supervision by MUSTAPHA HABIBI entitled Photoionization Of The Cerium Isonuclear Sequence And Cerium Endohedral Fullerene be accepted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Ronald A. Phaneuf, Ph. D., Advisor Jeffrey S. Thompson, Ph. D., Committee Member Peter Winkler, Ph. D., Committee Member Paul Neill, Ph. D., Committee Member Mohammed S. Fadali, Ph. D., Graduate School Representative Marsha H. Read, Ph. D., Associate Dean, Graduate School May, 2009 To the souls of my mother and my father, to my beloved wife and daughters, to all my family, friends and colleagues for their love and unconditional support. i Abstract This dissertation presents an experimental photoionization study of the cerium isonuclear sequence ions in the energy range of the 4d inner-shell giant resonance. In addition, single and double photoionization and photofragmentation cross sections of the cerium endohe- + dral ion Ce@C82 were also measured and studied in the 4d excitation-ionization energy range of cerium. Relative and absolute cross-section measurements were performed at un- dulator beamline 10.0.1 of the Advanced Light Source (ALS) for nine parent cerium ions: Ce+ { Ce9+. Double-to-single ionization cross-section ratios were measured for photoion- + + ization of the endohedral Ce@C82 and empty fullerene C82 molecular ions. -
Synthesis and Characterization of Non-IPR Monometallic Actinide
Article Cite This: J. Am. Chem. Soc. XXXX, XXX, XXX−XXX pubs.acs.org/JACS Synthesis and Characterization of Non-Isolated-Pentagon-Rule C ‑ Actinide Endohedral Metallofullerenes U@ 1(17418) C76, C ‑ C ‑ U@ 1(28324) C80, and Th@ 1(28324) C80: Low-Symmetry Cage Selection Directed by a Tetravalent Ion † § ⊥ ‡ ⊥ † ⊥ † ∥ † Wenting Cai, , , Laura Abella, , Jiaxin Zhuang, , Xingxing Zhang, Lai Feng, Yaofeng Wang, ‡ § # § Roser Morales-Martínez, Ronda Esper, Mauro Boero, Alejandro Metta-Magaña, ‡ ‡ § † Antonio Rodríguez-Fortea, Josep M. Poblet,*, Luis Echegoyen,*, and Ning Chen*, † Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, PR China ‡ Departament de Química Física i Inorganica,̀ Universitat Rovira i Virgili, c/Marcel·lí Domingo 1, 43007 Tarragona, Spain § Department of Chemistry, University of Texas at El Paso, 500 W University Avenue, El Paso, Texas 79968, United States # University of Strasbourg, CNRS, Institut de Physique et Chimie des Materiaux́ de Strasbourg UMR 7504, 23 rue du Loess, F-67034 Strasbourg, France ∥ Soochow Institute for Energy and Materials InnovationS (SIEMIS), College of Physics, Optoelectronics and Energy & Collaborative, Soochow University, Suzhou, Jiangsu 215006, PR China *S Supporting Information ABSTRACT: For the first time, actinide endohedral metal- lofullerenes (EMFs) with non-isolated-pentagon-rule (non-IPR) carbon cages, U@C80,Th@C80,andU@C76, have been successfully synthesized and fully characterized by mass spectrometry, single crystal X-ray diffractometry, UV−vis−NIR and Raman spectroscopy, and cyclic voltammetry. Crystallo- graphic analysis revealed that the U@C80 and Th@C80 share the same non-IPR cage of C1(28324)-C80, and U@C76 was assigned to non-IPR U@C1(17418)-C76. -
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. -
Structure of Endohedral Fullerene Eu@C74 W
View Online / Journal Homepage / Table of Contents for this issue PAPER www.rsc.org/pccp | Physical Chemistry Chemical Physics Structure of endohedral fullerene Eu@C74w Dmitrij Rappoport* and Filipp Furche Received 2nd February 2009, Accepted 12th May 2009 First published as an Advance Article on the web 10th June 2009 DOI: 10.1039/b902098e Structure determination of endohedral fullerenes in the absence of X-ray data is difficult and often controversial. Here we show that the structure of endohedral fullerene Eu@C74 may be determined by density functional theory aided interpretation of its electronic, infrared and Raman spectra. The use of recently developed analytical polarizability gradient methods to simulate resonance-enhanced Raman spectra is crucial for this approach and allows for a nearly complete assignment of the experimental spectra. Eu@C74 is assigned a pear-shaped C2v symmetric structure and shows strong ionic interaction between the encapsulated metal and the fullerene p system. 1. Introduction spectrum of Eu@C74 to predictions from time-dependent density functional theory (TDDFT) to identify the frontier Endohedral metallofullerenes constitute a large class of molecular orbitals, specifically the electronic configuration of fullerene inner complexes with metal atoms or small metal europium. The structure of the carbon cage is inferred from an clusters.1,2 Group 2 and 3 metals and lanthanides form a assignment of infrared and Raman spectra of Eu@C74. number of endohedral fullerene complexes notable for their An important tool in the structure elucidation of endohedral electronic absorption in the near infrared and for their large fullerenes is 13C nuclear magnetic resonance (NMR) spectro- 1–3 third-order nonlinear susceptibilities. -
Crystalline C60 Fulleride with Metal Inside
Crystalline C60 fulleride with metal inside Ayano Nakagawa1, Makiko Nishino1, Hiroyuki Niwa1, Katsuma Ishino1, Zhiyong Wang1, Haruka Omachi1, Ko Furukawa2, Takahisa Yamaguchi3, Tatsuhisa Kato3, Shunji Bandow4, Jeremy Rio5, Chris Ewels5, Shinobu Aoyagi6 & Hisanori Shinohara1* 1Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya 464-8602, Japan. 2Center for Coordination of Research Facilities, Institute for Research Promotion, Niigata University, Niigata 950-2181, Japan. 3Graduate School of Human and Environmental Sciences, Kyoto University, Sakyo-ku, Kyoto 606- 8501, Japan. 4Faculty of Science and Technology, Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan. 5Institut des Materiaux Jean Rouxel (IMN), Université de Nantes, CNRS UMR6502, BP3229, 44322 Nantes, France 6Department of Information and Basic Science, Nagoya City University, Nagoya 467-8501, Japan. Endohedral metallofullerenes have been extensively studied, since the first experimental observation of La@C60 in a laser-vaporized supersonic beam in 1985. However, all of these studies have been carried out on metallofullerenes larger than C60 such as (metal)@C82, and there + - are no reported purified C60-based metallofullerenes except for [Li@C60] (SbCl6) salt. Pure (metal)@C60 has not been obtained because of their extremely high chemical reactivity. We report here the first isolation, structural determination and electromagnetic properties of crystalline C60- based metallofullerenes, Gd@C60(CF3)5 and La@C60(CF3)5. Synchrotron X-ray single-crystal diffraction reveals that La and Gd atoms are indeed encapsulated in the Ih-C60 fullerene. The HOMO-LUMO gaps of Gd@C60 and La@C60 are significantly widened by an order of magnitude with addition of CF3- groups. Magnetic measurements show the presense of a weak antiferromagnetic coupling in Gd@C60(CF3)3 crystals at low temperatures. -
Endohedral Fullerenes: the Importance of Electronic, Size and Shape Complementarity Between the Carbon Cages and the Corresponding Encapsulated Clusters† Maira R
Research Article Received: 6 September 2013, Revised: 24 September 2013, Accepted: 6 October 2013, Published online in Wiley Online Library: 9 January 2014 (wileyonlinelibrary.com) DOI: 10.1002/poc.3245 Endohedral fullerenes: the importance of electronic, size and shape complementarity between the carbon cages and the corresponding encapsulated clusters† Maira R. Ceróna, Fang-Fang Lia and Luis A. Echegoyena* Cage-cluster complementarity is of crucial importance in determining the sizes and structures, as well as the properties of endohedral fullerenes. The encapsulated atoms or clusters, which are typically in a positively charged state, are irreversibly, mechanically, and electrostatically trapped inside the typically negatively charged cages. These rather exotic compounds exhibit exquisitely complementary properties between their components. Here, we present a short overview to show that size and shape are crucial in determining the specific structures that are formed, and the presence of electrostatic interactions result in structural motifs that are never observed for pristine fullerene cages. Copyright © 2014 John Wiley & Sons, Ltd. Keywords: electronic properties; endohedral fullerenes; fullerene and cluster cage sizes; fullerene and cluster shapes INTRODUCTION understand the most important factors involved in determining the specific structures that are observed and their relative importance. The discovery and increased interest and to some degree, fascina- tion of trapping and studying atoms and clusters inside the carbon cages -
Actinide-Based Endohedral Metallofullerenes
Actinide-Based Endohedral Metallofullerenes Bailey Bouley Literature Seminar November 14th, 2019 In 1985, Smalley, Curl, and Kroto synthesized a new allotrope of carbon, C60, by laser vaporization methods under a helium atmosphere.1 The discovery of the structure that formed, deemed buckminsterfullerene by the authors, along with the discovery of fullerenes of other sizes with Cn configurations, won them the Nobel Prize in Chemistry in 1996. Two weeks after their discovery, the same authors published the first example of a metal ion encapsulated within the cavity of a fullerene, La-Cn (n = 44 – 76), where the lower carbon count Cn configurations appeared to exhibit an increase in stability with the metal ion inclusion.2 This discovery sparked interest in chemical research focused on using these so-named endohedral metallofullerenes (EMFs) as a new approach to the construction of superconductors (for alkali metal EMFs),3 and as isolated environments to study fundamental principles of poorly understood f-block elements. The first actinide-containing EMF was discovered in 1992, when the authors hypothesized an appropriately sized tetravalent ion would be able to stabilize C28, a fullerene that had been previously detected by TOF-MS, but not isolated due to poor stability.4 The low stability of this cluster was attributed to the presence of highly reactive sites centralized on fused pentagon rings, systems that violated the isolated pentagon rule (IPR), which states that fullerenes containing fused 5 pentagon rings are destabilized due to high geometric strain. It was believed, and subsequently supported by DFT calculations, that non-IPR cages can be stabilized through an ionic model in which electrons are transferred from the metal atom to the cage itself, localizing negative charge on the reactive carbon center, resulting in stabilization of these sites.6,7 Figure 1. -
Nanotechnology - Fundamentals and Applications 1
D. Cremer, CHEM 6342, Nanotechnology - Fundamentals and Applications 1 CHEM 6342 Nanotechnology – Fundamentals and Applications Class location: TBD Lectures, time and location: TBD Lab times and location: TBD Instructor: Dieter Cremer, 325 FOSC, ext 8-1300, [email protected] http://smu.edu/catco/ Office Hours: By appointment Units: 3 Grading: ABC Letter Grade Class number TBD 1. Rationale: Nanotechnology (NT) is a rather young discipline, which came up in the nineties. Nevertheless, NT has gained so much importance within the last years that universities at all rankings have introduced or are going to introduce NT teaching programs. Predictions say that NT will change our lives and society more than computer technology and electricity have done together. The course will provide an overview over NT. It will show that the nano regime is so different from other regimes because both classical and quantum effects can be active thus leading to unique properties of nano devices. NT is a highly interdisciplinary science, which will be reflected in the course by making reference to chemistry, physics, biology, pharmacy, and engineering. Applications of NT, as they are already in use today or as they are planned for the future, will be discussed. 2. Course Recommendations: The course is designed to reach all graduate students who had have an education in chemistry, physics, engineering or biology. It does not require special knowledge in mathematics or theoretical physics. The course contents will be presented in self-sustained modules, which make it possible to follow the course without special knowledge. The course will prepare for the interdisciplinary work in NT. -
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. -
An Overview of Fullerene Chemistry
Bull. Mater. So., Vol. 20, No. 2, April 1997, pp. 141-230. © Printed in India. An overview of fullerene chemistry S SAMAL* and S K SAHOO Department of Chemistry, gavenshawCollege, Cuttack 753 003, India MS received 4 April 1996; revised 3 October 1996 Abstract. Fullerenes which were thought to be 'superaromatics' are actually 'super- alkenes'. Reactions in fuUerenesare varied, ranging from the addition of simple molecules like H 2 to large moleculeslike dendrimers.The synthesis,structure, characterization,along with simple reactions like halogenation, oxygenation, metalation,cydoaddition, polymeri- zation and dendrimer addition are discussed. Keywards. Fullerenes;C6o; C7o; characterization;reactions. 1. Introduction Fullerenes and their derivatives possess a number of potentially useful physical, biological and chemical properties. Our interest in the chemistry of fullerenes led us to present this review in which we have attempted to furnish an overall picture of the properties of these novel molecules. The scope of the review is however limited. The conclusion of the authors contributing to this rapidly growing field of research are accepted and presented in a concise manner highlighting the salient features of the original work. The technique developed by Kr/itschmer et al (1990) for preparing and isolating macroscopic quantities of C6o, 'a new form of carbon', opened the way for exploring the molecular and bulk properties of these novel species. Kroto et al (1985) reported the nature and chemical reactivity of C6o species produced during the nucleation of carbon plasma. C6o , which was found to be stable, was named buckminsterfullerene after Buckminster Fuller, American architect, engineer and constructor of geodesic dome. -
Self-Assembled Fullerene Nanostructures Lok Kumar Shrestha1* , Rekha Goswami Shrestha2, Jonathan P
Journal of Oleo Science Copyright ©2013 by Japan Oil Chemists’ Society J. Oleo Sci. 62, (8) 541-553 (2013) REVIEW Self-Assembled Fullerene Nanostructures Lok Kumar Shrestha1* , Rekha Goswami Shrestha2, Jonathan P. Hill1 and Katsuhiko Ariga1, 3 1 World Premier International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044 JAPAN 2 Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science 2641 Yamazaki, Noda, Chiba 278- 8510, JAPAN 3 PRESTO & CREST, JST, 1-1 Namiki, Tsukuba 305-0044 JAPAN Abstract: This review briefly summarizes recent developments in fabrication techniques of shape-controlled nanostructures of fullerene crystals across different length scales and the self-assembled mesostructures of functionalized fullerenes both in solutions and solid substrates. Key words: fullerene, self-assembly, nanostructures, liquid-liquid interfacial precipitation, nanowhiskers, nanotubes, nanosheets 1 INTRODUCTION compose an icosohedra(l Ih)symmetric closed cage struc- Design of nanostructured materials whose properties ture of the C60 molecule(diameter~0.8 nm). In C60, each can be tailored across different length scales so that they carbon atom is bonded to three other carbon atoms can be utilized in different functional systems and nanode- through sp2 hybridized bonds with the tendency for double vices fabrication is a current topic of great interest in the bonds not to be present at the pentagonal rings resulting in field of materials nanoarchitectonics. Self-assembly is one poor electron delocalization, i.e. C60 is not a superaromatic of the special techniques applied for the organization of molecule. As a result, it behaves as an electron deficient functional molecules such as fullerenes, amphiphiles, pro- molecule. -
Synthesis of Modified Fullerenes for Oxygen Reduction Reactions
Journal of Materials Chemistry A View Article Online PAPER View Journal | View Issue Synthesis of modified fullerenes for oxygen reduction reactions† Cite this: J. Mater. Chem. A,2016,4, 14284 a a bc a Rosa Mar´ıa Giron,´ Juan Marco-Mart´ınez, Sebastiano Bellani, Alberto Insuasty, Hansel Comas Rojas,bd Gabriele Tullii,b Maria Rosa Antognazza,*b a ae Salvatore Filippone* and Nazario Mart´ın* The oxygen reduction reaction (ORR) is a key process common in several energy converting systems or electro-chemical technologies such as fuel cells, metal–air batteries, oxygen sensors, etc., which is based on the use of expensive and scarcely available platinum metal. In the search for carbon-based catalysts for ORRs, two different classes of new fullerene hybrids and metal-free fullerene derivatives endowed with suitable active sites have been prepared by highly selective metal- and organo-catalyzed synthetic methodologies. Along with their classical behavior as electron acceptors in polymer-based Received 1st August 2016 photo-electrochemical cells, the new fullerene derivatives are able to efficiently catalyze ORRs by using Accepted 15th August 2016 no metals or very low amounts of metals. Remarkably, the activity of metal-free fullerenes has proved to Creative Commons Attribution-NonCommercial 3.0 Unported Licence. DOI: 10.1039/c6ta06573b be as high as that observed for metallofullerenes bearing noble metals, and up to ten-fold higher than www.rsc.org/MaterialsA that of PCBM. 1 Introduction capability led to their extended use as suitable n-type