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Endohedral Metallofullerenes

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (1 May 2017) | Viewed by 15129

Special Issue Editor

Department of Materials, University of Oxford, Parks road, Oxford OX1 3PH, UK
Interests: synthesis and characterization of carbon nanomaterials; endohedral nitrogen fullerenes and endohedral metallofullerenes; fundamentals of the mechanisms of formation of several endohedral fullerene species; carbon nanotube-fullerene hybrids; polymer-nanoparticle interactions; reactivity of fullerenes and development of novel fullerene adducts with emphasis in quantum nanoelectronics, medical applications, and energy harvesting via organic photovoltaics
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Special Issue Information

Dear Colleagues,

Fullerenes represent a rare example of spherical molecules with a hollow interior space. Their discovery in 1985 by Kroto, Smalley, Curl, and their co-workers opened up a new avenue of research in nanomaterials. The structure of fullerenes was later verified unequivocally by experimental and theoretical data. This led to Kroto, Smalley, and Curl being awarded the Nobel Prize in Chemistry in 1996.

It is the ability of fullerene molecules to act as hosts for a variety of atoms, clusters and molecules that makes them unique within many aspects of organic chemistry. Almost immediately after the discovery of fullerenes, lanthanum was incorporated in fullerene cages. Since then, a large number of group-2, 3, and 4 elements have been inserted in different fullerenes. In addition, group-15 elements (nitrogen and phosphorous) and inert gases (helium, argon, etc.) have also been successfully encapsulated and the list keeps growing. These molecules are called endohedral fullerenes. The term endohedral is derived from the Greek prefix ένδο- (endo—inside) and the Greek word έδρα (hedra—facet of a geometrical shape) reflecting on the geometrical attributes of fullerenes. In a tour-de-force synthetic effort, it was also shown that molecular surgery methods could be used to insert whole molecules, such as H2, H2O and NH3, inside fullerenes.

Out of all the different types of endohedral fullerenes, endohedral metallofullerenes, i.e., fullerenes with a number of metals inside them have been produced over time in macroscopic quantities and good yields. Metallofullerenes can be synthesized via the well-established DC arc discharge method, previously developed for empty cage synthesis and this gives them an edge compared to other endohedral fullerene species. Apart from the good production yields these molecules are also attractive for another reason: The metal(s) inside the fullerene, interact(s) with the cage. As a result, a number of valence electrons are transferred to the cage from the metal and a hybrid molecule is formed with significant dipole or quadruple moment present that alters the electronic configuration of the cage and increases the functionality of fullerenes.

In this Special Issue “Endohedral Metallofullerenes” in Molecules we shall focus on the physical and chemical properties of these fascinating molecules with the aim to sample some of the latest results regarding metallofullerene research and their potential for energy, medical and optoelectronic applications.

Prof. Dr. Kyriakos Porfyrakis
Guest Editor

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Keywords

  • Nanomaterials
  • Fullerenes
  • Endohedral
  • Metallofullerenes
  • Metal-cage interactions
  • Charge-transfer
  • Stability
  • Spectroscopy
  • Chemical functionalization
  • Energy harvesting
  • Optoelectronics

Published Papers (3 papers)

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Research

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845 KiB  
Article
Eu@C72: Computed Comparable Populations of Two Non-IPR Isomers
by Zdeněk Slanina, Filip Uhlík, Shigeru Nagase, Takeshi Akasaka, Ludwik Adamowicz and Xing Lu
Molecules 2017, 22(7), 1053; https://doi.org/10.3390/molecules22071053 - 24 Jun 2017
Cited by 22 | Viewed by 3789
Abstract
Relative concentrations of six isomeric Eu@C 72 —one based on the IPR C 72 cage (i.e., obeying the isolated-pentagon rule, IPR), two cages with a pentagon–pentagon junction (symmetries C 2 and C 2 v ), a cage with one heptagon, a cage with [...] Read more.
Relative concentrations of six isomeric Eu@C 72 —one based on the IPR C 72 cage (i.e., obeying the isolated-pentagon rule, IPR), two cages with a pentagon–pentagon junction (symmetries C 2 and C 2 v ), a cage with one heptagon, a cage with two heptagons, and a cage with two pentagon–pentagon fusions—are DFT computed using the Gibbs energy in a broad temperature interval. It is shown that the two non-IPR isomers with one pentagon–pentagon junction prevail at any relevant temperature and exhibit comparable populations. The IPR-satisfying structure is disfavored by both energy and entropy. Full article
(This article belongs to the Special Issue Endohedral Metallofullerenes)
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Review

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3540 KiB  
Review
Functionalization of Endohedral Metallofullerenes with Reactive Silicon and Germanium Compounds
by Masahiro Kako, Shigeru Nagase and Takeshi Akasaka
Molecules 2017, 22(7), 1179; https://doi.org/10.3390/molecules22071179 - 14 Jul 2017
Cited by 9 | Viewed by 5103
Abstract
Exohedral derivatization of endohedral metallofullerenes (EMFs) has been exploited as a useful method for characterizing the structural and chemical properties of EMFs, and for functionalizing them for potential applications. The introduction of heteroatoms, such as electropositive silicon atoms, to fullerene cages is a [...] Read more.
Exohedral derivatization of endohedral metallofullerenes (EMFs) has been exploited as a useful method for characterizing the structural and chemical properties of EMFs, and for functionalizing them for potential applications. The introduction of heteroatoms, such as electropositive silicon atoms, to fullerene cages is a novel functionalization method that remarkably affects the electronic characteristics of fullerenes. This review comprehensively describes the results of the reactions of monometallofullerene, dimetallofullerene, and trimetallic nitride template EMFs with disilirane, silirane, silylene, and digermirane, which afforded the corresponding silylated and germylated fullerenes. Several examples emphasize that exohedral functionalization regulates the dynamic behaviors of the encapsulated metal atoms and clusters in the fullerene cages. The electronic effects of silyl and germyl groups are represented by comparing the redox properties of silylated and germylated EMFs with those of other EMFs derivatized with carbon-atom-based functional groups. Full article
(This article belongs to the Special Issue Endohedral Metallofullerenes)
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2236 KiB  
Review
Non-Chromatographic Purification of Endohedral Metallofullerenes
by Zhiyong Wang, Haruka Omachi and Hisanori Shinohara
Molecules 2017, 22(5), 718; https://doi.org/10.3390/molecules22050718 - 29 Apr 2017
Cited by 8 | Viewed by 5679
Abstract
The purification of endohedral metallofullerenes by high performance liquid chromatography is very time-consuming and expensive. A number of rapid and inexpensive non-chromatographic methods have thus been developed for large-scale purification of metallofullerenes. In this review, we summarize recent advances in non-chromatographic purification methods [...] Read more.
The purification of endohedral metallofullerenes by high performance liquid chromatography is very time-consuming and expensive. A number of rapid and inexpensive non-chromatographic methods have thus been developed for large-scale purification of metallofullerenes. In this review, we summarize recent advances in non-chromatographic purification methods of metallofullerenes. Lewis acid-based complexation is one of the most efficient and powerful methods for separation of metallofullerenes from empty fullerenes. The first oxidation potential of metallofullerenes is a critical factor that affects the separation efficiency of the Lewis acid-based method. Supramolecular methods are effective for separation of fullerenes and metallofullerenes that are different in size and shape. Chemical/electrochemical reduction and exohedral functionalization are also utilized to separate and purify metallofullerenes on a large scale. Full article
(This article belongs to the Special Issue Endohedral Metallofullerenes)
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