Endohedral fullerene

Endohedral fullerenes, also called endofullerenes, are fullerenes that have additional atoms, ions, or clusters enclosed within their inner spheres. The first lanthanum C60 complex was synthesized in 1985 and called La@C60. The @ (at 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. Endohedral fullerenes, also called endofullerenes, are fullerenes that have additional atoms, ions, or clusters enclosed within their inner spheres. The first lanthanum C60 complex was synthesized in 1985 and called La@C60. The @ (at 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. In a traditional chemical formula notation, a buckminsterfullerene (C60) with an atom (M) was simply represented as MC60 regardless of whether M was inside or outside the fullerene. In order to allow for more detailed discussions with minimal loss of information, a more explicit notation was proposed in 1991, where the atoms listed to the left of the @ sign are situated inside the network composed of the atoms listed to the right. The example above would then be denoted M@C60 if M were inside the carbon network. A more complex example is K2(K@C59B), which denotes 'a 60-atom fullerene cage with one boron atom substituted for a carbon in the geodesic network, a single potassium trapped inside, and two potassium atoms adhering to the outside.' The choice of the symbol has been explained by the authors as being concise, readily printed and transmitted electronically (the at sign is included in ASCII, which most modern character encoding schemes are based on), and the visual aspects suggesting the structure of an endohedral fullerene. 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 1999 a discovery drew large attention. With the synthesis of the Sc3N@C80 by Harry Dorn and coworkers, 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. 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 +6@−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). The lack of reactivity in Diels-Alder reactions is utilised in a method to purify −6 compounds from a complex mixture of empty and partly filled fullerenes of different cage size. 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 +6@−6 pass through the column unreacted. In Ce2@C80 the two metal atoms exhibit a non-bonded interaction. Since all the six-membered rings in C80-Ih are equal the two encapsulated Ce atoms exhibit a three-dimensional random motion. 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. Martin Saunders in 1993 produced endohedral complexes He@C60 and Ne@C60 by pressurizing C60 to ca. 3 bar in a noble-gas atmosphere. 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 with pressures of 3 kbars and incorporation of up to 0.1% of the noble gases.