Purification of endohedral trimetallic nitride fullerenes in a single, facile step

Abstract

A major hurdle hampering the development of fullerenes, endohedral metallofullerenes, and nanotubes has been the difficulty of obtaining high purity samples. Soots prepared in the usual manner via a Krätschmer-Huffman electric-arc generator consist of mixtures of insoluble carbonaceous materials and soluble fullerenes: C60, C70, C76, C78, C84, etc. When metals are introduced as endohedral species the complexity of the resultant soot is even greater because of the presence of multiple isomers of both the empty fullerenes and the endohedral metallofullerenes. Here, for the first time, we report that lanthanide trimetallic nitride endohedral metallofullerenes, A3N@C80 (A = lanthanide atom, e.g., Er, Gd, Ho, Lu, Sc, Tb, Tm, Y), can be obtained in pure form directly from as-prepared soots in a single facile step by taking advantage of their extraordinary kinetic chemical stability with respect to the other fullerenes in Diels-Alder reactions with a cyclopentadiene-functionalized resin. We show that careful control of conditions (stoichiometry, time, temperature) allows separation of fullerenes with different cage sizes, as well as isomeric species. Furthermore, the Diels-Alder reaction is thermally reversible, and we demonstrated that the bound empty-cage fullerenes and classical endohedral metallofullerenes can be recovered by displacement with maleic anhydride.