Endohedral Metallofullerenes

Dear Colleagues,

Fullerenes represent a rare example of spherical molecules with a hollow interior space. Their discovery in 1985 by Kroto, Smalley, Curl, and their co-workers opened up a new avenue of research in nanomaterials. The structure of fullerenes was later verified unequivocally by experimental and theoretical data. This led to Kroto, Smalley, and Curl being awarded the Nobel Prize in Chemistry in 1996.

It is the ability of fullerene molecules to act as hosts for a variety of atoms, clusters and molecules that makes them unique within many aspects of organic chemistry. Almost immediately after the discovery of fullerenes, lanthanum was incorporated in fullerene cages. Since then, a large number of group-2, 3, and 4 elements have been inserted in different fullerenes. In addition, group-15 elements (nitrogen and phosphorous) and inert gases (helium, argon, etc.) have also been successfully encapsulated and the list keeps growing. These molecules are called endohedral fullerenes. The term endohedral is derived from the Greek prefix ένδο- (endo—inside) and the Greek word έδρα (hedra—facet of a geometrical shape) reflecting on the geometrical attributes of fullerenes. In a tour-de-force synthetic effort, it was also shown that molecular surgery methods could be used to insert whole molecules, such as H₂, H₂O and NH₃, inside fullerenes.

Out of all the different types of endohedral fullerenes, endohedral metallofullerenes, i.e., fullerenes with a number of metals inside them have been produced over time in macroscopic quantities and good yields. Metallofullerenes can be synthesized via the well-established DC arc discharge method, previously developed for empty cage synthesis and this gives them an edge compared to other endohedral fullerene species. Apart from the good production yields these molecules are also attractive for another reason: The metal(s) inside the fullerene, interact(s) with the cage. As a result, a number of valence electrons are transferred to the cage from the metal and a hybrid molecule is formed with significant dipole or quadruple moment present that alters the electronic configuration of the cage and increases the functionality of fullerenes.

In this Special Issue “Endohedral Metallofullerenes” in Molecules we shall focus on the physical and chemical properties of these fascinating molecules with the aim to sample some of the latest results regarding metallofullerene research and their potential for energy, medical and optoelectronic applications.

Prof. Dr. Kyriakos Porfyrakis
Guest Editor

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