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Fullerene molecule with additional atoms, ions, or clusters enclosed within itself

Endohedral fullerenes, also called endofullerenes, are fullerenes that have additional atoms, ions, or clusters enclosed within their inner spheres. The first lanthanum C60 complex called La@C60 was synthesized in 1985. 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,

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). 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. Since all the six membered rings in C80 Ih are equal 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. Gd@C82(OH)22, an endohedral metallofluorenol, can competitively inhibit the WW domain in the oncogene YAP1 from activating. It was originally developed as an MRI contrast agent.

Endohedral complexes He@C60 and Ne@C60 are prepared 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. 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 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. Noble gas endofullerenes are predicted to exhibit 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.,. The sign of the Δα polarizability exaltation depends on the number of atoms in a fullerene molecule: for small fullerenes , it is positive; for the larger ones , it is negative (depression of polarizability). The following formula, describing the dependence of Δα on n, has been proposed: 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" ).

Closed fullerenes encapsulating small molecules have been synthesized. Representative are the synthesis of the dihydrogen endofullerene H2@C60, the water endofullerene H2O@C60, the hydrogen fluoride endofullerene HF@C60, and the methane endofullerene CH4@C60. The encapsulated molecules display unusual physical properties which have been studied by a variety of physical methods. As shown theoretically, compression of molecular endofullerenes (e. g., H2@C60) may lead to dissociation of the encapsulated molecules and reaction of their fragments with interiors of the fullerene cage. Such reactions should result in endohedral fullerene adducts, which are currently unknown.