Fullerenes Revisited
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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. -
Competitive Retro-Cycloaddition Reaction in Fullerene Dimers Connected Through Pyrrolidinopyrazolino Rings
pubs.acs.org/joc Competitive Retro-Cycloaddition Reaction in Fullerene Dimers Connected through Pyrrolidinopyrazolino Rings Juan Luis Delgado,†,‡ Sı´lvia Osuna,§ Pierre-Antoine Bouit,‡ Roberto Martı´nez-Alvarez,† Eva Espı´ldora,† Miquel Sola,* ,§ and Nazario Martı´n*,†,‡ †Departamento de Quı´mica Organica, Facultad de Ciencias Quı´micas, Universidad Complutense de Madrid, E-28040, Madrid, Spain, ‡IMDEA-Nanociencia, Facultad de Ciencias, Modulo C-IX, 3a planta, Ciudad Universitaria de Cantoblanco, E-29049 Madrid, Spain, and §Institut de Quı´mica Computacional and Departament de Quı´mica, Universitat de Girona, E-17071 Girona, Catalonia, Spain [email protected]; [email protected] Received July 31, 2009 Competitive retro-cycloaddition in [60]- and [70]fullerene homodimers (1a,1c) as well as [60]/[70]heterodimer (1b), linked through 2-pyrazolinopyrrolidino bridges, has been studied by means of HPLC, mass spectrometry, and theoretical calculations at the density functional theory (DFT) level by using the two-layered ONIOM approach. The results of these investigations indicate that the retro-cycloaddition reaction of pyrrolidinofullerenes is favored compared to the retro- cycloaddition reaction of 2-pyrazolinofullerenes in compounds 1a-c. Evidence of the occurrence of this process have been observed both by HPLC and MS-MALDI, these findings being in good agreement with those predicted by theoretical calculations. Introduction variety of new reactions.4 Some of us have previously reported the thermally induced transition metal catalyzed Since fullerenes1 and other molecular carbon nanostruc- tures2 were discovered, a remarkable effort has been devoted 3 (3) (a) Hirsch A. The Chemistry of Fullerenes; Wiley-VCH: Weinheim, to their chemical modification. Moreover, owing to their Germany, 2005. -
Recent Advances in Electrochemical Biosensors Based on Fullerene-C60 Nano-Structured Platforms
Biosensors 2015, 5, 712-735; doi:10.3390/bios5040712 OPEN ACCESS biosensors ISSN 2079-6374 www.mdpi.com/journal/biosensors/ Review Recent Advances in Electrochemical Biosensors Based on Fullerene-C60 Nano-Structured Platforms Sanaz Pilehvar * and Karolien De Wael AXES Research Group, Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium; E-Mail: [email protected] * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +32-3265-3338. Academic Editors: Prabir Patra and Ashish Aphale Received: 9 September 2015 / Accepted: 14 October 2015 / Published: 23 November 2015 Abstract: Nanotechnology is becoming increasingly important in the field of (bio)sensors. The performance and sensitivity of biosensors is greatly improved with the integration of nanomaterials into their construction. Since its first discovery, fullerene-C60 has been the object of extensive research. Its unique and favorable characteristics of easy chemical modification, conductivity, and electrochemical properties has led to its tremendous use in (bio)sensor applications. This paper provides a concise review of advances in fullerene-C60 research and its use as a nanomaterial for the development of biosensors. We examine the research work reported in the literature on the synthesis, functionalization, approaches to nanostructuring electrodes with fullerene, and outline some of the exciting applications in the field of (bio)sensing. Keywords: nanotechnology; nanostructures; nano-bio hybrids; fullerene-biomolecule; biosensors 1. Introduction Bio-nanotechnology is a new emerging field of nanotechnology and combines knowledge from engineering, physics, and molecular engineering with biology, chemistry, and biotechnology aimed at the development of novel devices, such as biosensors, nanomedicines, and bio-photonics [1]. -
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. -
Rsc Cc C3cc46247a 3..5
ChemComm View Article Online COMMUNICATION View Journal | View Issue An effective retro-cycloaddition of M3N@C80 Cite this: Chem. Commun., 2013, (M = Sc, Lu, Ho) metallofulleropyrrolidines† 49, 10489 Bo Wu,a Taishan Wang,a Zhuxia Zhang,a Yongqiang Feng,a Lihua Gan,b Li Jianga Received 15th August 2013, and Chunru Wang*a Accepted 17th September 2013 DOI: 10.1039/c3cc46247a www.rsc.org/chemcomm Sc3N@C80 fulleropyrrolidines are typical metallofullerene deriva- Echegoyen et al. proposed the isolation of metallofullerenes by an 16 tives which were generated by the reaction of Sc3N@C80 with electrochemical method. In this communication, we report N-trityloxazolidinone. Here we report an effective retro-reaction of a reversible cycloaddition reaction for TNT metallofullerenes, Sc3N@C80 fulleropyrrolidine by using 3-chloroperoxybenzoic acid which is considered to be a promising separation technique for to give pristine Sc3N@C80 in a high yield. This technique is metallofullerenes. expected to be used for separating metallofullerenes (M3N@C80) It is well known that the 1,3-dipolar cycloaddition reaction from hollow fullerenes without HPLC. between (metallo)fullerenes and azomethine ylides (Prato reac- tion) is widely used to prepare various (metallo)fulleropyr- Endohedral metallofullerenes (EMFs) are novel nanomaterials rolidines.17–19 Moreover, the retro-cycloaddition reactions of with stable nesting structures and unique electronic proper- fulleropyrrolidines and metallofulleropyrrolidines are also of ties.1–4 In this family, tri-metallic nitride template (TNT) cluster- great concern as the cycloaddition reversibility is related to 5–7 21 fullerenes, such as Sc3N@C80,Gd3N@C80,andLu3N@C80,have their yield optimization and recycling of metallofullerenes. -
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.