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. 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.
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 (4S3/2) 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 phosphorus complexes) or by direct ion implantation. Alternatively, endohedral hydrogen fullerenes can be produced by opening and closing a fullerene by organic chemistry methods. A recent example of endohedral fullerenes includes single molecules of water encapsulated in C60.
According to state-of-the-art DFT calculations, noble gas endofullerenes should demonstrate unusual polarizability. Thus, calculated values of mean polarizability of Ng@C60 do not equal to the sum of polarizabilities of a fullerene cage and the trapped atom, i.e. exaltation of polarizability occurs.,. As shown in, the sign of the Δα polarizability exaltation depends on the number of atoms in a fullerene molecule: for small fullerenes (n<30), it is positive; for the larger ones (n>30), it is negative (depression of polarizability). Sabirov has proposed the following formula, describing the dependence of Δα on n: Δα = αNg(2e–0.06(n – 20)-1) . It describes the DFT-calculated mean polarizabilities of Ng@C60 endofullerenes with sufficient accuracy. The calculated data allows using C60 fullerene as a Faraday cage, which isolates the encapsulated atom from the external electric field. The mentioned relations should be typical for the more complicated endohedral structures (e.g., C60@C240 and giant fullerene-containing onions ).
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