Endohedral fullerenes

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Endohedral fullerenes are fullerenes that have additional atoms, ions, or clusters enclosed within their inner spheres. The first lanthanum C60 complex was synthesed in 1985 called La@C60. The @ sign in the name reflects the notion of a small molecule trapped inside a shell. Two types of endohedral complexes exist: endohedral metallofullerenes and non-metal doped fullerenes [1].

[edit] Endohedral metallofullerenes

Doping fullerenes with electropositive metals takes place in an arc reactor or via laser evaporation. The metals can be transition metals like scandium, yttrium as well as lanthanides like lanthanum and cerium. Also possible are endohedral complexes with elements of the alkaline earth metals like barium and strontium, alkali metals like potassium and tetravalent metals like uranium, zirconium and hafnium. The synthesis in the arc reactor is however unspecific. Besides unfilled fullerenes, endohedral metallofullerenes develop with different cage sizes like La@C60 or La@C82 and as different isomer cages. Aside from the dominant presence of mono-metal cages, numerous di-metal endohedral complexes and the tri-metal carbide fullerenes like Sc3C2@C80 were also isolated.

In 1998 a discovery drew large attention. With the synthesis of the Sc3N@C80, the inclusion of a molecule fragment in a fullerene cage had succeeded for the first time, . This compound can be prepared by arc-vaporization at temperatures up to 1100 °C of graphite rods packed with Scandium(III) oxide iron nitride and graphite powder in a K-H generator in a nitrogen atmosphere at 300 Torr [2].

Endohedral metallofullerenes are characterised by the fact that electrons will transfer from the metal atom to the fullerene cage and that the metal atom takes a position off-center in the cage. The size of the charge transfer is not always simple to determine. In most cases it is between 2 and 3 charge units, in the case of the La2@C80 however it can be even about 6 electrons such as in Sc3N@C80 which is better described as [Sc3N]+6@[C80]-6. These anionic fullerene cages are very stable molecules and do not have the reactivity associated with ordinary empty fullerenes. They are stable in air up to very high temperatures (600 to 850°C) and the Prato reaction yields only a monoadduct and not multi-adducts as with empty fullerenes.

The lack of reactivity in Diels-Alder reactions is utilised in a method to purify [C80]-6 compounds from a complex mixture of empty and partly filled fullerenes of different cage size [2]. In this method Merrifield resin is modified as a cyclopentadienyl resin and used as a solid phase against a mobile phase containing the complex mixture in a column chromatography operation. Only very stable fullerenes such as [Sc3N]+6@[C80]-6 pass through the column unreacted.

In Ce2@C80 the metal atoms are found to be untouchable and display a three-dimensional random motion [3]. This is evidenced by the presence of only two signals in the 13C-NMR spectrum. It is possible to force the metal atoms to a standstill at the equator as shown by x-ray crystallography when the fullerene is exahedrally functionalized by an electron donation silyl group in a reaction of Ce2@C80 with 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disilirane.

[edit] Non-metal doped fullerenes

Saunders in 1993 could prove the existence of the endohedral complexes He@C60 and Ne@C60 which form when C60 is exposed to a pressure of around 3 bar of the noble gases [4]. Under these conditions it was possible to dope one out of every 650,000 C60 cages with a helium atom. In the meantime the formation of endohedral complexes with helium, neon, argon, krypton and xenon as well as numerous adducts of the He@C60 compound could also be proven [5] with operating pressures of 3000 bars and incorporation of up to 0.1 % of the noble gases.

While noble gases are chemically inert and therefore always occur as a single atom, the discovery that this is also the case with nitrogen and phosphorus in endohedral complexes is very unusual. Proven and isolated thus far are the complexes N@C60, N@C70 and P@C60. The nitrogen atom here is in its electronic initial state (4S3/2) and is therefore to be regarded as highly reactive. Nevertheless N@C60 is so stable that exohedral derivatization is possible from the mono- to the hexa adduct of the malonic acid ethyl ester. In these compounds no charge transfer of the nitrogen atom in the center to the carbon atoms of the cage takes place. Therefore 13C-couplings, which are observed very easily with the endohedral Metallofullerenes, could only be proven in the case of the N@C60 with a high resolution as shoulders of the central line.

The central atom In the case of noble gases and nitrogen and/or phosphorus is located exactly in the center of the endohedral complex. While other atomic traps are realized normally with large machine expenditure, e.g. by laser cooling of atoms or ions or in magnetic traps, endohedral fullerenes represent an atomic trap at room temperature and for an arbitrarily long time. Atomic or ion traps are of great interest since particles are present here without any reciprocal effect from their environment . In this way the intrinsic properties of these particles can be observed. One of these characteristics is the compression of the atomic wave function as a consequence of the packing in the cage which could be observed with ENDOR spectroscopy. The nitrogen atom can be used as a probe, in order to detect the smallest changes of the electronic structure of its environment. Contrary to the metallo endohedral compounds these complexes cannot be produced in an arc. Production starts from unfilled fullerenes as raw material and the atoms are implanted. The synthesis of nitrogen and/or phosphor endohedral fullerenes occurs by gas discharge or by direct ion implantation.

Endohedral hydrogen fullerenes can be produced by a third method namely by opening and closing a fullerene by organic chemistry methods.

[edit] References

  1. ^ Periodic table of endohedral fullerene atoms
  2. ^ a b Purification of Endohedral Trimetallic Nitride Fullerenes in a Single, Facile Step Zhongxin Ge, James C. Duchamp, Ting Cai, Harry W. Gibson, and Harry C. Dorn J. Am. Chem. Soc.; 2005; 127(46) pp 16292 - 16298; (Article) DOI: 10.1021/ja055089t Abstract
  3. ^ Positional Control of Encapsulated Atoms Inside a Fullerene Cage by Exohedral Addition Michio Yamada, Tsukasa Nakahodo, Takatsugu Wakahara, Takahiro Tsuchiya, Yutaka Maeda, Takeshi Akasaka, Masahiro Kako, Kenji Yoza, Ernst Horn, Naomi Mizorogi, Kaoru Kobayashi, Shigeru Nagase J. Am. Chem. Soc.; 2005; 127(42) pp 14570 - 14571 DOI: 10.1021/ja054346r Graphical Abstract
  4. ^ Stable compounds of helium and neon. He@C60 and Ne@C60. M. Saunders, H. A. Jiménez-Vázquez, R. J. Cross y R. J. Poreda, Science 1993, 259, 1428–1430
  5. ^ Incorporation of helium, neon, argon, krypton, and xenon into fullerenes using high pressure Martin Saunders, Hugo A. Jimenez-Vazquez, R. James Cross, Stanley Mroczkowski, Michael L. Gross, Daryl E. Giblin, and Robert J. Poreda J. Am. Chem. Soc.; 1994; 116(5) pp 2193 - 2194; DOI:10.1021/ja00084a089
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