Angewandte Chemie International Edition

Cover image for Vol. 56 Issue 10

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemPhotoChem, ChemPlusChem, Zeitschrift für Chemie

Fullerenes: Discovery and Current Progress

Harry W. Kroto passed away on April 30th 2016. Kroto shared the 1996 Nobel Prize in Chemistry with Robert Curl and Richard Smalley for their work on the discovery of fullerenes. These species have since become an integral part of chemistry and related fields, with applications in photovoltaics, biology, liquid crystals, molecular electronics, and supramolecular chemistry. Although the area was established more than 25 years ago, it is still continually expanding.

This virtual issue of Angewandte Chemie coincides with the Memorial Lecture given by Nazario Martín at the EuCheMS Chemistry Congress in Seville. It starts with some classic papers that describe the discovery and early years of the field, including Kroto's seminal Review from 1992 and the Nobel Lectures by Kroto, Curl, and Smalley. It also contains some of our most recently published articles that show just how productive the field of fullerene chemistry currently is.

Sir Harold Walter Kroto (1939–2016)

Sir Harold Walter Kroto (1939–2016)

Anthony J. Stace*

The Nobel Laureate Harry Kroto passed away aged 76 on April 30, 2016. His name will always be associated with the discovery of C60 , for which he was awarded the Nobel Prize in Chemistry 1996 together with Rick Smalley and Robert Curl. Experiments designed to aid the discovery of molecules in space ultimately led to an entirely new branch of condensed-phase physics and chemistry.

Angew. Chem. Int. Ed. 10.1002/anie.201604585 [Obituary]

The Third Allotropic Form of Carbon

The Third Allotropic Form of Carbon

J. Fraser Stoddart*

For many chemists, the molecules of the year 1990 are C60 and C70. The recent report of an efficient route of preparation—organic chemists might disagree with the word synthesis—has sparked numerous investigations into the structure, chemical reactivity, and electro- and photochemical behavior of these species. In 1991, we can expect to learn much more about this third modification of carbon (the picture on the right, which shows crystals of C70 (actually cornflower blue) was provided by F. Diederich, Los Angeles).

Angew. Chem. Int. Ed. 1991, 30, No. 1, 70–71 [Highlight]

C60: Buckminsterfullerene, The Celestial Sphere that Fell to Earth

C60: Buckminsterfullerene, The Celestial Sphere that Fell to Earth

Harold W. Kroto*

A “round organic chemistry” has burgeoned this last year following the development of an efficient means of producing fullerenes in 1989/1990. One of the protoganists in the fullerene story describes in a lively personal style how this fascinating new chemistry came about. In this thriller he points out that the discovery of C60 in 1985 did not result from an applications-oriented search but rather from basic research and scientific curiosity.

Angew. Chem. Int. Ed. 1992, 31, No. 2, 111–129 [Review]

A Highly Symmetric Sixfold Cycloaddition Product of Fullerene C60

A Highly Symmetric Sixfold Cycloaddition Product of Fullerene C60

Bernhard Kräutler*, Josef Maynollo

In one step and with 26% yield, a sixfold Diels-Alder product is formed from buckminsterfullerene C60 and 2,3-dimethyl-1,3-butadiene. This first direct synthesis of a highly symmetric, exohedrally sixfold substituted fullerene addition product is remarkably simple. The components were heated in ortho-dichlorobenzene at roughly 110°C for ten days, and the product was purified by column chromatography.

Angew. Chem. Int. Ed. 1995, 34, No. 1, 87–88 [Communication]

Fullerene–Oligonucleotide Conjugates: Photoinduced Sequence-Specific DNA Cleavage

Fullerene–Oligonucleotide Conjugates: Photoinduced Sequence‐Specific DNA Cleavage

Alexandre S. Boutorine, Masashi Takasugi, Claude Hélène*, Hidetoshi Tokuyama, Hiroyuki Isobe, Eiichi Nakamura

The guanine-specific cleavage of oligonucleotides is achieved with the conjugate 1, which contains a fullerene tethered to a tetradecadeoxyribonucleotide Nu(pNu)n. This conjugate was able to form a duplex with a complementary oligonucleotide, and triplexes with appropriate double-stranded oligonucleotides. Irradiation of the complexes leads to site-specfic cleavage of the target sequences—probably through the action of singlet oxygen.

Angew. Chem. Int. Ed. 1995, 33, No. 23-24, 2462–2465 [Communication]

Dawn of Fullerenes: Conjecture and Experiment (Nobel Lecture)

Robert F. Curl*

Although counterintuitive, the conjecture that high-symmetry, low-entropy truncated icosahedron C60 spontaneously forms out of the chaos of condensing carbon vapor proved to be true. The observation that the cluster of 60 carbon atoms is singularly chemically unreactive, as exemplified by its flagpole prominence in mass spectra, could be explained only by this hypothesis. This resulted in more conjecture, some of which proved correct, whereas others relating C60 to diffuse interstellar bonds and soot formation remain speculative. Even if of questionable validity, these speculations have played a useful role in driving chemists to think about the formation of fullerenes and other carbon morphologies.

Angew. Chem. Int. Ed. 1997, 36, No. 15, 1566–1576 [Review]

Symmetry, Space, Stars, and C60 (Nobel Lecture)

Harold Kroto*

Basic research must continue to be supported! This is one of the conclusions clearly evident from the story behind the discovery of the fullerenes. The questions to which answers were originally sought would not have been posed within the current confines of programs aimed increasingly at applied research. This and the fascination associated with C60 and other members of the fullerene family are the central messages in this Nobel lecture.

Angew. Chem. Int. Ed. 1997, 36, No. 15, 1578–1593 [Review]

Discovering the Fullerenes (Nobel Lecture)

Richard E. Smalley*

Bucky get the prize—eleven years after the discovery of C60 in 1985, the realization that carbon makes this truncated isosahedral molecule, and larger geodesic cages, all by itself is honored with the Nobel Prize. Only with the development of laser-vaporization cluster beam methods did the particular signification of C60 become apparent. Indeed the discovery process with respect to fullerenes and the properties of carbon is far from being complete.

Angew. Chem. Int. Ed. 1997, 36, No. 15, 1594–1601 [Review]

Richard E. Smalley: Fullerenes

Harold Kroto

Angew. Chem. Int. Ed. 2006, 45, No. 1, 26–27 [Obituary]

The Covalent Chemistry of Higher Fullerenes: C70 and Beyond

The Covalent Chemistry of Higher Fullerenes: C70 and Beyond

Carlo Thilgen, Andreas Herrmann, François Diederich*

The chemistry of higher fullerenes is no longer on the sidelines. Seven years after fullerenes became available on a preparative scale, the functionalization of the higher homologues of buck minsterfullerene C60—in particular C70, but also C76, C78 (a tris-adduct is shown on the right as an example), and C84—has made considerable progress. It has now been reviewed for the first time under particular consideration of the aspects of chirality and some emerging reactivity principles.

Angew. Chem. Int. Ed. 1997, 36, No. 21, 2268–2280 [Review]

Spherical Aromaticity in Ih Symmetrical Fullerenes: The 2(N+1)2 Rule

Andreas Hirsch, Zhongfang Chen, Haijun Jiao

The maximal spherical aromaticity of an icosahedral fullerene such as C202+ (see picture) can only be achieved with 2(N+1)2 π electrons. There is clear evidence for this rule from the magnetic behavior of the endohedral He complexes on the basis of 3He NMR chemical shifts and it is ascribed to the spherical charge distribution.

Angew. Chem. Int. Ed. 2000, 39, No. 21, 3915–3917 [Communication]

New Cages and Unusual Guests: Fullerene Chemistry Continues To Excite

New Cages and Unusual Guests: Fullerene Chemistry Continues To Excite

Andreas Hirsch

Minifullerenes, bizarre cages, and highly reactive guests are currently causing a stir in fullerene chemistry. An example is C20, recently generated in the gas phase, which constitutes the smallest conceivable classical fullerene.

Angew. Chem. Int. Ed. 2001, 40, No. 7, 1195–1197 [Highlight]

Isolation and Structural Characterization of the Endohedral Fullerene Sc3N@C78

Isolation and Structural Characterization of the Endohedral Fullerene Sc3N@C78

Marilyn M. Olmstead, Ana de Bettencourt-Dias, James C. Duchamp, Steven Stevenson, Daniela Marciu, Harry C. Dorn, Alan L. Balch

The unfavorable D3hisomer of the C78 fullerene cage is present in Sc3N@C78, an endohedral fullerene which has been prepared by the trimetallic nitride template process. The crystal structure of the fullerene–porphyrin adduct Sc3N@C78⋅[Co(oep)]⋅1.5 C6H6⋅0.3 CHCl3 (oep=octaethylporphyrin) shows that the scandium atoms are located over the centers of the [6,6] ring junctions of pyracylene patches on the inner surface of the fullerene (see picture).

Angew. Chem. Int. Ed. 2001, 40, No. 7, 1223–1225 [Communication]

Insertion of Helium and Molecular Hydrogen Through the Orifice of an Open Fullerene

Insertion of Helium and Molecular Hydrogen Through the Orifice of an Open Fullerene

Yves Rubin, Thibaut Jarrosson, Guan-Wu Wang, Michael D. Bartberger, K. N. Houk, Georg Schick, Martin Saunders, R. James Cross

A “molecular surgery” approach has been used to create an opening within a fullerene cage that is large enough to allow atoms and small molecules to pass through. The thermodynamics for the insertion of He and H2 into the open fullerene (left and right pictures, respectively) as well as their escape have been studied by NMR spectroscopy and theoretical methods.

Angew. Chem. Int. Ed. 2001, 40, No. 8, 1543–1546 [Communication]

Efficient Methano[70]fullerene/MDMO-PPV Bulk Heterojunction Photovoltaic Cells

Efficient Methano[70]fullerene/MDMO‐PPV Bulk Heterojunction Photovoltaic Cells

Martijn M. Wienk, Jan M. Kroon, Wiljan J. H. Verhees, Joop Knol, Jan C. Hummelen, Paul A. van Hal, René A. J. Janssen

Owing to their increased absorption of light in the visible region, [70]fullerene derivatives provide a high photocurrent when incorporated as the electron acceptor in thin-film polymer photovoltaic cells. An incident-photon-to-current efficiency of 66 % is obtained when [70]PCBM (see picture) is used in combination with a poly(p-phenylene vinylene). These high currents originate from an ultrafast charge transfer that occurs upon photoexcitation of either the fullerene or the polymer.

Angew. Chem. Int. Ed. 2003, 42, No. 29, 3371–3375 [Communication]

Fullerene-Terminated Dendritic Multiporphyrin Arrays: “Dendrimer Effects” on Photoinduced Charge Separation

Fullerene‐Terminated Dendritic Multiporphyrin Arrays: “Dendrimer Effects” on Photoinduced Charge Separation

Myung-Seok Choi, Takuzo Aida, Hongxia Luo, Yasuyuki Araki, Osamu Ito

Energy funnels: A large dendritic zinc porphyrin heptamer (7PZn) in a C60-terminated electron-transfer relay system 7PZn-C60 (see picture) not only harvests visible light for the electron transfer to the C60 terminus, but also retards the back-electron-transfer process, thus resulting in a longer lifetime of the charge-separated state (7Pequation image-Cequation image).

Angew. Chem. Int. Ed. 2003, 42, No. 34, 4060–4063 [Communication]

Methods for the Chemical Synthesis of Fullerenes

Methods for the Chemical Synthesis of Fullerenes

Lawrence T. Scott

From corannulene to C60: Geodesic polyarenes can be synthesized in the laboratory by bending flat molecules and stitching them up into molecular bowls, baskets, and balls, using rational chemical methods.

Angew. Chem. Int. Ed. 2004, 43, No. 38, 4994–5007 [Review]

Hydrogen-Bonding Motifs in Fullerene Chemistry

Hydrogen‐Bonding Motifs in Fullerene Chemistry

Luis Sánchez, Nazario Martín, Dirk M. Guldi

Supramolecular chemistry of C60 is leading the way for the use of C60 as a unique photo- and electroactive building block. Arrays of hydrogen bonds ensure a high degree of order on the nanometer scale, a feature that will be critical in the application of the resulting noncovalently bound ensembles as molecular materials or supramolecular catalysts (see scheme; eT=electron transfer, ET=energy transfer).

Angew. Chem. Int. Ed. 2005, 44, No. 34, 5374–5382 [Minireview]

Fullerenes: Multitask Components in Molecular Machinery

Fullerenes: Multitask Components in Molecular Machinery

Aurelio Mateo-Alonso, Dirk M. Guldi, Francesco Paolucci, Maurizio Prato

A multipurpose component: Owing to their size and unique properties, fullerenes, and especially C60, have found applications in molecular machines, for example, as stoppers in rotaxanes. C60 has been introduced in molecular shuttles as an electro- and photoactive stopper that is able to induce and modulate shuttling through π–π interactions.

Angew. Chem. Int. Ed. 2007, 46, No. 43, 8120–8126 [Minireview]

Polymer–Fullerene Composite Solar Cells

Polymer–Fullerene Composite Solar Cells

Barry C. Thompson, Jean M. J. Fréchet

Energy from the sun: Polymer–fullerene (P3HT–PCBM) solar cells have attracted a great deal of attention recently as a result of reports of devices with efficiencies approaching 5 %. The current state-of-the-art in the field is critically examined with a focus on the lessons learned on the electronic and morphological interactions of the polymer and the fullerene, and the areas where improvements still need to be made for the optimization of such devices.

Angew. Chem. Int. Ed. 2008, 47, No. 1, 58–77 [Review]

Glycosidase Inhibition with Fullerene Iminosugar Balls: A Dramatic Multivalent Effect

Glycosidase Inhibition with Fullerene Iminosugar Balls: A Dramatic Multivalent Effect

Philippe Compain, Camille Decroocq, Julien Iehl, Michel Holler, Damien Hazelard, Teresa Mena Barragán, Carmen Ortiz Mellet, Jean-François Nierengarten

Superball! A dodecavalent iminosugar derivative with a fullerene core (see picture) shows a binding enhancement of up to three orders of magnitude over the corresponding monovalent ligand in glycosidase inhibition assays. This is the first evidence of a significant multivalent effect in glycosidase inhibition.

Angew. Chem. Int. Ed. 2010, 49, No. 33, 5753–5756 [Communication]

Hierarchical Selectivity in Fullerenes: Site-, Regio-, Diastereo-, and Enantiocontrol of the 1,3-Dipolar Cycloaddition to C70

Hierarchical Selectivity in Fullerenes: Site‐, Regio‐, Diastereo‐, and Enantiocontrol of the 1,3‐Dipolar Cycloaddition to C70

Enrique E. Maroto, Abel de Cózar, Salvatore Filippone, Ángel Martín-Domenech, Margarita Suarez, Fernando P. Cossío*, Nazario Martín*

Make your choice of stereochemistry: The first enantioselective cycloaddition of N-metalated azomethine ylides to the C70 molecule affords both pyrrolidino[70]fullerene enantiomers, with ee values over 90 %, depending on the chiral metal complex used (see picture). The high site- and regioselectivity observed has been accounted for by the nucleophilic and electrophilic Fukui indexes determined by theoretical calculations.

Angew. Chem. Int. Ed. 2011, 50, No. 27, 6060–6064 [Communication]

Wraparound Hosts for Fullerenes: Tailored Macrocycles and Cages

Wraparound Hosts for Fullerenes: Tailored Macrocycles and Cages

David Canevet, Emilio M. Pérez, Nazario Martín*

All wrapped up: In the field of fullerene recognition, chemists are currently facing new challenges dealing with the selective extraction of higher fullerenes, their chiral resolution, or their organization in molecular materials. In this regard, the new generation of macrocyclic hosts looks particularly promising and has already allowed important breakthroughs.

Angew. Chem. Int. Ed. 2011, 50, No. 40, 9248–9259 [Minireview]

Liquid-Crystalline Hybrid Materials Based on [60]Fullerene and Bent-Core Structures

Liquid‐Crystalline Hybrid Materials Based on [60]Fullerene and Bent‐Core Structures

Jorge Vergara, Joaquín Barberá, José Luis Serrano, M. Blanca Ros*, Nerea Sebastián, Rosario de la Fuente, David O. López, Gustavo Fernández, Luis Sánchez, Nazario Martín

What a core-ker! By the appropriate combination of promesogenic bent-core structures and the C60 unit, lamellar polar liquid-crystal phases were induced (see scheme). The supramolecular organization of the functional fullerene-based assemblies, the temperature range of the soft phase, the stabilization of the mesophase-like order at room temperature, and the molecular switching under an electric field can be tuned, depending on the molecular structure.

Angew. Chem. Int. Ed. 2011, 50, No. 52, 12523–12528 [Communication]

Formation of Heterofullerenes by Direct Exposure of C60 to Boron Vapor

Formation of Heterofullerenes by Direct Exposure of C60 to Boron Vapor

Paul W. Dunk, Antonio Rodríguez-Fortea, Nathan K. Kaiser, Hisanori Shinohara, Josep M. Poblet*, Harold W. Kroto*

Introducing boron: Heterofullerenes that incorporate boron have been scarcely studied because a formation route from C60 is not known. It is now reported that C59B, an electronically closed-shell species, is formed directly from pristine C60 in the gas-phase by facile atom exchange reactions.

Angew. Chem. Int. Ed. 2013, 52, No. 1, 315–319 [Communication]

Gating Charge Recombination Rates through Dynamic Bridges in Tetrathiafulvalene–Fullerene Architectures

Gating Charge Recombination Rates through Dynamic Bridges in Tetrathiafulvalene–Fullerene Architectures

Sonia Castellanos, Andre A. Vieira, Beatriz M. Illescas, Valentina Sacchetti, Christina Schubert, Javier Moreno, Dirk M. Guldi*, Stefan Hecht*, Nazario Martín*

An open and shut case: The competition between charge separation and recombination in artificial photosynthetic systems can be controlled by using photochromic dynamic bridge. The photoinduced opening and closing of the bridge mediates the electronic coupling between donor (D) and acceptor (A).

Angew. Chem. Int. Ed. 2013, 52, No. 52, 13985–13990 [Communication]

Electron Transfer in a Supramolecular Associate of a Fullerene Fragment

Electron Transfer in a Supramolecular Associate of a Fullerene Fragment

María Gallego, Joaquín Calbo, Juan Aragó, Rafael M. Krick Calderon, Fernando H. Liquido, Takahiro Iwamoto, Allison K. Greene, Edward A. Jackson, Emilio M. Pérez, Enrique Ortí*, Dirk M. Guldi*, Lawrence T. Scott*, Nazario Martín*

Bowl meets bowl: The association of a fullerene fragment, hemifullerene C30H12, with an electron-donating bowl-shaped tetrathiafulvalene derivative (truxTTF) has been investigated. Electron transfer from truxTTF to C30H12 to form the fully charge-separated species takes place upon irradiation of the associate with light, constituting the first example in which a fullerene fragment mimics the electron-accepting behavior of the fullerenes within a supramolecular complex.

Angew. Chem. Int. Ed. 2014, 53, No. 8, 2170–2175 [Communication]

Regioselective Electrosynthesis of Rare 1,2,3,16-Functionalized [60]Fullerene Derivatives

Regioselective Electrosynthesis of Rare 1,2,3,16‐Functionalized [60]Fullerene Derivatives

Yang Xiao, San-E Zhu, Ding-Jia Liu, Mitsuaki Suzuki, Xing Lu*, Guan-Wu Wang*

Exercizing control: The highly regioselective reaction of dianionic fullerene species, generated by electroreduction of a fulleroindoline, with benzyl bromide or ethyl bromoacetate affords the rare 1,2,3,16-adducts of C60 (see scheme). Intriguingly, either one or two alkyl groups can be selectively introduced onto the fullerene surface in the absence or presence of sodium hydride. The high regioselectivity is governed by both the charge distribution and steric factors.

Angew. Chem. Int. Ed. 2014, 53, No. 11, 3006–3010 [Communication]

High Degree of Polymerization in a Fullerene-Containing Supramolecular Polymer

High Degree of Polymerization in a Fullerene‐Containing Supramolecular Polymer

Helena Isla, Emilio M. Pérez*, Nazario Martín*

Tight embrace makes polymers longer: A self-recognizing monomer containing a fullerene guest and an exTTF-based macrocyclic host self-assembles to form linear supramolecular polymers with an extreme degree of polymerization. Polymers of MW up 90 kDa in the gas phase and over 150 kDa in solution have been detected. These materials might find use in the construction of self-organized optoelectronic devices, where polymers of high molecular weight are typically found to yield more efficient devices.

Angew. Chem. Int. Ed. 2014, 53, No. 22, 5629–5633 [Communication]

Supramolecular [60]Fullerene Liquid Crystals Formed By Self-Organized Two-Dimensional Crystals

Supramolecular [60]Fullerene Liquid Crystals Formed By Self‐Organized Two‐Dimensional Crystals

Xiaoyan Zhang, Chih-Hao Hsu, Xiangkui Ren, Yan Gu, Bo Song, Hao-Jan Sun, Shuang Yang, Erqiang Chen, Yingfeng Tu*, Xiaohong Li, Xiaoming Yang, Yaowen Li, Xiulin Zhu*

Soft materials: A series of fullerene dyads self-organize to form two-dimensional crystals through π–π interactions between fullerenes. Lamellar packing of the 2D crystals gives rise to the formation of a new family of thermotropic supramolecular liquid crystals with hierarchical structures.

Angew. Chem. Int. Ed. 2015, 54, No. 1, 114–117 [Communication]

Nanoporous Carbon Tubes from Fullerene Crystals as the π-Electron Carbon Source

Nanoporous Carbon Tubes from Fullerene Crystals as the π‐Electron Carbon Source

Lok Kumar Shrestha*, Rekha Goswami Shrestha, Yusuke Yamauchi*, Jonathan P. Hill, Toshiyuki Nishimura, Kun'ichi Miyazawa, Takazumi Kawai, Susumu Okada, Katsunori Wakabayashi, Katsuhiko Ariga*

Thermal conversion of 1D fullerene (C60) single-crystal nanorods and nanotubes gives nanoporous carbon materials with retention of the initial 1D morphology. The nanoporous carbon materials exhibit π-electron conjugation within the sp2-carbon robust frameworks and show excellent electrochemical capacitance and superior sensing properties for aromatic compounds.

Angew. Chem. Int. Ed. 2015, 54, No. 3, 951–955 [Communication]

Metal-Atom Impact on the Self-Assembly of Cup-and-Ball Metalloporphyrin–Fullerene Conjugates

Metal‐Atom Impact on the Self‐Assembly of Cup‐and‐Ball Metalloporphyrin–Fullerene Conjugates

Luis Moreira, Joaquín Calbo, Beatriz M. Illescas, Juan Aragó, Iwona Nierengarten, Béatrice Delavaux-Nicot, Enrique Ortí*, Nazario Martín*, Jean-François Nierengarten*

The pearl in the oyster: The influence of the metal atom in the overall stability of a series of cup-and-ball complexes formed by a crown porphyrin and a fullerene ammonium derivative is evaluated. The combination of experimental and in silico studies provides a deep insight into the nature of the porphyrin–fullerene interaction.

Angew. Chem. Int. Ed. 2015, 54, No. 4, 1255–1260 [Communication]

Guest-Induced Transformation of a Porphyrin-Edged FeII4L6 Capsule into a CuIFeII2L4 Fullerene Receptor

Guest‐Induced Transformation of a Porphyrin‐Edged FeII4L6 Capsule into a CuIFeII2L4 Fullerene Receptor

Daniel M. Wood, Wenjing Meng, Tanya K. Ronson, Artur R. Stefankiewicz, Jeremy K. M. Sanders, Jonathan R. Nitschke*

An accommodating host: The combination of a bent nickel(II) porphyrin containing bis-bidentate ligand and FeII yielded an FeII4L6 cage that undergoes a structural transformation in the presence of different fullerenes. The new product is an FeII3L4 cone-shaped assembly with a fullerene bound inside its central cavity. The simultaneous addition of CuI and fullerene leads to the formation of an unprecedented CuIFeII2L4 heterometallic host–guest complex.

Angew. Chem. Int. Ed. 2015, 54, No. 13, 3988–3992 [Communication]

A Perfect Match: Fullerene Guests in Star-Shaped Oligophenylenevinylene Mesogens

A Perfect Match: Fullerene Guests in Star‐Shaped Oligophenylenevinylene Mesogens

Matthias Lehmann*, Markus Hügel

Come into my arms: Stilbenoid star-shaped mesogens pack densely, in helical structures that have a short correlation length, in columnar liquid-crystal phases. Attaching a fullerene guest to the interior of the star fills the void space between the arms and considerably increases the mesophase stability by approximately 70 °C. The stabilization is the result of the formation of a fullerene triple helix.

Angew. Chem. Int. Ed. 2015, 54, No. 13, 4110–4114 [Communication]

Charge Separation in Graphene-Decorated Multimodular Tris(pyrene)–Subphthalocyanine–Fullerene Donor–Acceptor Hybrids

Charge Separation in Graphene‐Decorated Multimodular Tris(pyrene)–Subphthalocyanine–Fullerene Donor–Acceptor Hybrids

Chandra B. KC, Gary N. Lim, Francis D'Souza*

In a split second: Ultrafast photochemical charge separation in multimodular donor–acceptor systems, composed of three units of pyrene, a subphthalocyanine, and a fullerene hybridized on graphene through π–π stacking interactions, is demonstrated using femtosecond transient spectroscopy. The present hybrids may have use as materials for fast-responding optoelectronic devices and in light energy harvesting applications.

Angew. Chem. Int. Ed. 2015, 54, No. 17, 5088–5092 [Communication]

Construction of a Hemifullerene Skeleton: A Regioselective Intramolecular Oxidative Cyclization

Construction of a Hemifullerene Skeleton: A Regioselective Intramolecular Oxidative Cyclization

Toru Amaya*, Takanori Ito, Toshikazu Hirao*

Bowl full of π: The two-step synthesis of a strained π bowl, having a hemifullerene skeleton from sumanene, was achieved in a high yield. The reaction involved a regioselective intramolecular oxidative cyclization as the key reaction. This cyclization is regioselective and is likely to be under thermodynamic control.

Angew. Chem. Int. Ed. 2015, 54, No. 18, 5483–5487 [Communication]

A Highly-Ordered 3D Covalent Fullerene Framework

A Highly‐Ordered 3D Covalent Fullerene Framework

Norma K. Minar, Kun Hou, Christian Westermeier, Markus Döblinger, Jörg Schuster, Fabian C. Hanusch, Bert Nickel, Geoffrey A. Ozin, Thomas Bein*

Self-assembling C60: A highly ordered 3 D fullerene framework is prepared with a structure based on octahedrally functionalized fullerene building blocks. The C60 building blocks coassemble with a liquid-crystalline block copolymer to produce a covalent fullerene framework with orthorhombic Fmmm symmetry and 7.5 nm pores.

Angew. Chem. Int. Ed. 2015, 54, No. 26, 7577–7581 [Communication]

Isolation and Structure Determination of a Missing Endohedral Fullerene La@C70 through In Situ Trifluoromethylation

Isolation and Structure Determination of a Missing Endohedral Fullerene La@C70 through In Situ Trifluoromethylation

Zhiyong Wang, Shinobu Aoyagi, Haruka Omachi, Ryo Kitaura, Hisanori Shinohara*

The missing link: The molecular structure of a missing metallofullerene La@C70 was determined for the first time through in situ trifluoromethylation of the fullerene cage, followed by single-crystal X-ray diffraction. La@C70 is greatly stabilized as a consequence of trifluoromethylation-induced bandgap enlargement.

Angew. Chem. Int. Ed. 2016, 55, No. 1, 199–202 [Communication]

A DNA–Fullerene Conjugate as a Template for Supramolecular Chromophore Assemblies: Towards DNA-Based Solar Cells

A DNA–Fullerene Conjugate as a Template for Supramolecular Chromophore Assemblies: Towards DNA‐Based Solar Cells

Philipp Ensslen, Stefan Gärtner, Konstantin Glaser, Alexander Colsmann, Hans-Achim Wagenknecht*

DNA in solar cells: A chromophore assembly of ethynyl Nile red and ethynyl pyrene, templated and ordered by a single-stranded DNA–fullerene conjugates, shows light-harvesting properties and photovoltaic activity. This work demonstrates that DNA is suitable as a structural element for chromophore assemblies in future organic optoelectronic devices, such as solar cells.

Angew. Chem. Int. Ed. 2016, 55, No. 5, 1904–1908 [Communication]

New Isolated-Pentagon-Rule and Skeletally Transformed Isomers of C100 Fullerene Identified by Structure Elucidation of their Chloro Derivatives

New Isolated‐Pentagon‐Rule and Skeletally Transformed Isomers of C100 Fullerene Identified by Structure Elucidation of their Chloro Derivatives

Song Wang, Shangfeng Yang*, Erhard Kemnitz*, Sergey I. Troyanov*

Chloride is key: Three isomers of C100 fullerene which obey the isolated pentagon rule (IPR) have been isolated and characterized by X-ray structure determination of their chloro derivatives. Although the IPR cages in C1-C100(425)Cl22 and C2-C100(18)Cl28/30 retain cage connectivities, Cs-C100(417)Cl28 transforms into the nonclassical (NC) isomer C1-C98(NC)Cl26 by loss of a C2 fragment (see picture; C=gray; Cl=green).

Angew. Chem. Int. Ed. 2016, 55, No. 10, 3451–3454 [Communication]

Structural Polymorphism and Thin Film Transistor Behavior in the Fullerene Framework Molecule 5,6;11,12-di-o-Phenylenetetracene

Structural Polymorphism and Thin Film Transistor Behavior in the Fullerene Framework Molecule 5,6;11,12‐di‐o‐Phenylenetetracene

Tobias Wombacher, Andrea Gassmann, Sabine Foro, Heinz von Seggern, Jörg J. Schneider*

When polymorphism rules: The orientation of individual molecules of a peri substituted acene with cross-conjugated π-systems differs significantly in its single-crystal and thin film structure. In the latter, a most efficient face-to-face overlap arranges its individual arene moieties in a slipped stacking mode resulting in a close π-π overlap. This gives rise to attractive hole carrier mobilities and decent thin film transistor properties.

Angew. Chem. Int. Ed. 2016, 55, No. 20, 6041–6046 [Communication]

Fulleretic Well-Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

Derek E. Williams, Ekaterina A. Dolgopolova, Danielle C. Godfrey, Evgeniya D. Ermolaeva, Perry J. Pellechia, Andrew B. Greytak, Mark D. Smith, Stanislav M. Avdoshenko, Alexey A. Popov*, Natalia B. Shustova*

Photophysics: In a crystalline metal–donor–fullerene framework the donor–fullerene mutual orientation is controlled through metal coordination. Because of ultrafast energy and electron transfer, fulleretic materials will contribute not only to the basic science of fullerene chemistry, but also be used for developments in photovoltaics and molecular electronics.

Angew. Chem. Int. Ed. 2016, 55, No. 31, 9070–9074 [Communication]

Regio-, Stereo-, and Atropselective Synthesis of C60 Fullerene Bisadducts by Supramolecular-Directed Functionalization

Regio‐, Stereo‐, and Atropselective Synthesis of C60 Fullerene Bisadducts by Supramolecular‐Directed Functionalization

Giovanni Bottari*, Olga Trukhina, Axel Kahnt, Michael Frunzi, Yasujiro Murata, Antonio Rodríguez-Fortea, Josep M. Poblet, Dirk M. Guldi*, Tomás Torres*

E pluribus unum: A conceptually novel, supramolecular-directed functionalization approach is presented in which noncovalent interactions between untethered residues have been used to amplify (>2800-fold) the regio-, stereo-, and atropselective formation of a C60 fullerene bisadduct racemate. Remarkably, both enantiomers represent the first examples of fullerene derivatives with combined central, axial, and helical chirality.

Angew. Chem. Int. Ed. 10.1002/anie.201602713 [Communication]

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