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Polyarenes II

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About this book

Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.

Table of Contents

Frontmatter
Buckyballs
Abstract
Buckyballs represent a new and fascinating molecular allotropic form of carbon that has received a lot of attention by the chemical community during the last two decades. The unabating interest on this singular family of highly strained carbon spheres has allowed the establishing of the fundamental chemical reactivity of these carbon cages and, therefore, a huge variety of fullerene derivatives involving [60] and [70]fullerenes, higher fullerenes, and endohedral fullerenes have been prepared. Much less is known, however, of the chemistry of the uncommon non-IPR fullerenes which currently represent a scientific curiosity and which could pave the way to a range of new fullerenes. In this review on buckyballs we have mainly focused on the most recent and novel covalent chemistry of fullerenes involving metal catalysis and asymmetric synthesis, as well as on some of the most significant advances in supramolecular chemistry, namely H-bonded fullerene assemblies and the search for efficient concave receptors for the convex surface of fullerenes. Furthermore, we have also described the recent advances in the macromolecular chemistry of fullerenes, that is, those polymer molecules endowed with fullerenes which have been classified according to their chemical structures. This review is completed with the study of endohedral fullerenes, a new family of fullerenes in which the carbon cage of the fullerene contains a metal, molecule, or metal complex in the inner cavity. The presence of these species affords new fullerenes with completely different properties and chemical reactivity, thus opening a new avenue in which a more precise control of the photophysical and redox properties of fullerenes is possible. The use of fullerenes for organic electronics, namely in photovoltaic applications and molecular wires, complements the study and highlights the interest in these carbon allotropes for realistic practical applications. We have pointed out the so-called non-IPR fullerenes – those that do not follow the isolated pentagon rule – as the most intriguing class of fullerenes which, up to now, have only shown the tip of the huge iceberg behind the examples reported in the literature. The number of possible non-IPR carbon cages is almost infinite and the near future will show us whether they will become a reality.
Juan L. Delgado, Salvatore Filippone, Francesco Giacalone, Ma Ángeles Herranz, Beatriz Illescas, Emilio M. Pérez, Nazario Martín
Carbon Nanotubes: Synthesis, Structure, Functionalization, and Characterization
Abstract
Carbon nanotubes have generated great expectations in the scientific arena, mainly due to their spectacular properties, which include a high aspect ratio, high strain resistance, and high strength, along with high conductivities. Nowadays, carbon nanotubes are produced by a variety of methods, each of them with advantages and disadvantages. Once produced, carbon nanotubes can be chemically modified, using a wide range of chemical reactions. Functionalization makes these long wires much easier to manipulate and dispersible in several solvents. In addition, the properties of carbon nanotubes can be combined with those of organic appendages. Finally, carbon nanotubes need to be carefully characterized, either as pristine or modified materials.
Valeria Anna Zamolo, Ester Vazquez, Maurizio Prato
Three-Dimensional Aromatic Networks
Abstract
Three-dimensional (3D) networks consisting of aromatic units and linkers are reviewed from various aspects. To understand principles for the construction of such compounds, we generalize the roles of building units, the synthetic approaches, and the classification of networks. As fundamental compounds, cyclophanes with large aromatic units and aromatic macrocycles with linear acetylene linkers are highlighted in terms of transannular interactions between aromatic units, conformational preference, and resolution of chiral derivatives. Polycyclic cage compounds are constructed from building units by linkages via covalent bonds, metal-coordination bonds, or hydrogen bonds. Large cage networks often include a wide range of guest species in their cavity to afford novel inclusion compounds. Topological isomers consisting of two or more macrocycles are formed by cyclization of preorganized species. Some complicated topological networks are constructed by self-assembly of simple building units.
Graphical Abstract
Shinji Toyota, Tetsuo Iwanaga
Antiaromaticity in Nonbenzenoid Oligoarenes and Ladder Polymers
Abstract
Polycyclic aromatic hydrocarbons (PAHs) and fully-conjugated ladder polymers are leading candidates for organics electronics, as their inherent conformational rigidity encourages electron delocalization. Many of these systems consist of fused benzenoid or heterocyclic aromatic rings. Less frequently, however, PAHs are reported with character that alternates between the aromaticity of benzene fragments and the antiaromaticity of a nonbenzenoid moiety. This chapter will focus on recent work published on the theory, synthesis, and properties of two such systems: [N]phenylenes containing 4π-electron cyclobutadienoid character, and diaryl[a,e]pentalenes containing 8π-electron pentalenoid character.
Rebecca R. Parkhurst, Timothy M. Swager
Stereochemistry of Bistricyclic Aromatic Enes and Related Polycyclic Systems
Abstract
Abstract
Bistricyclic aromatic enes (BAEs) and related polycyclic systems are a class of molecular materials that display a rich variety of conformations, dynamic stereochemistry and switchable chirality, color, and spectroscopic properties. This is due to the a subtle interplay of the inherent preference for planarity of aromatic systems and the competing necessity of non-planarity due to intramolecular overcrowding in the fjord regions built into the general molecular structure of BAEs. The conformational, dynamic, and spectroscopic properties may be designed and fine-tuned, e.g., by variation of the bridging groups X and Y, the overcrowding in the fjord regions, extensions of the aromatic system, or other modifications of the general BAE structure, based on the fundamental understanding of the structure–property relationships (SPR). The present review provides an analysis of the conformational spaces and the dynamic stereochemistry of overcrowded bistricyclic aromatic enes applying fundamental symmetry considerations. The symmetry analysis presented here allows deeper insight into the conformations, chirality, and the mechanisms of the dynamic stereochemistry, and will be instrumental in future computational studies.
Graphical Abstract
P. Ulrich Biedermann, Israel Agranat
Backmatter
Metadata
Title
Polyarenes II
Editors
Jay S. Siegel
Yao-Ting Wu
Copyright Year
2014
Electronic ISBN
978-3-319-07302-6
Print ISBN
978-3-319-07301-9
DOI
https://doi.org/10.1007/978-3-319-07302-6

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