Endohedral fullerenes

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].

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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.

Non-metal doped fullerenes

Saunders in 1993 showed the formation of endohedral complexes He@C₆₀ and Ne@C₆₀ when C₆₀ is exposed to a pressure of around 3 bar of the noble gases^[4]. Under these conditions about one out of every 650 000 C₆₀ cages was doped with a helium atom. The formation of endohedral complexes with helium, neon, argon, krypton and xenon as well as numerous adducts of the He@C₆₀ compound was also demonstrated^[5] with pressures of 3000 bars and incorporation of up to 0.1% of the noble gases.

While noble gases are chemically very inert and commonly exist as individual atoms, this is not the case for nitrogen and phosphorus and so the formation of the endohedral complexes N@C₆₀, N@C₇₀ and P@C₆₀ is more surprising. The nitrogen atom is in its electronic initial state (⁴S_3/2) and is therefore to be highly reactive. Nevertheless N@C₆₀ is sufficiently stable that exohedral derivatization from the mono- to the hexa adduct of the malonic acid ethyl ester is possible. 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 observed in the case of the N@C₆₀ in a high resolution spectrum as shoulders of the central line.

The central atom in these endohedral complexes is located in the center of the cage. While other atomic traps require complex equipment, e.g. laser cooling or magnetic traps, endohedral fullerenes represent an atomic trap that is stable at room temperature and for an arbitrarily long time. Atomic or ion traps are of great interest since particles are present free from (significant) interaction with their environment, allowing unique quantum mechanical phenomena to be explored. For example, the compression of the atomic wave function as a consequence of the packing in the cage 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. Atoms are implanted in the fullerene starting material using gas discharge (nitrogen and phosphorous complexes) or by direct ion implantation. Alternatively, endohedral hydrogen fullerenes can be produced by opening and closing a fullerene by organic chemistry methods.

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. ^ M. Saunders, H. A. Jiménez-Vázquez, R. J. Cross, and R. J. Poreda (1993). "Stable compounds of helium and neon. He@C60 and Ne@C60". Science 259: 1428–1430.
5. ^ Martin Saunders, Hugo A. Jimenez-Vazquez, R. James Cross, Stanley Mroczkowski, Michael L. Gross, Daryl E. Giblin, and Robert J. Poreda (1994). "Incorporation of helium, neon, argon, krypton, and xenon into fullerenes using high pressure". J. Am. Chem. Soc. 116 (5): 2193-2194. doi:10.1021/ja00084a089.