With the successful isolation of TiSc(2)N@C(80), the first Ti-containing nitride clusterfullerene (NCF), a non-group-III metal is stabilized in a NCF for the first time.

The recently isolated TiSc(2)N@C(80) was used to study the spin state of a Ti(3+) ion in a mixed metal nitride cluster in a fullerene cage. The electronic state of the new clusterfullerene is characterized starting with the redox behavior of this structure. It differs markedly from that of homometallic nitride clusterfullerenes in giving reversible one-electron transfers even on the cathodic scale. Both oxidation and reduction of TiSc(2)N@C(80) occur at the endohedral cluster changing the valence state of Ti from Ti(II) in anion to Ti(IV) in cation. The unpaired electron in TiSc(2)N@C(80) is largely fixed at the Ti ion as shown by low temperature ESR measurements. Isotropic g-factor 1.9454 points to the significant spin-orbit coupling with an unquenched orbital momentum of the 3d electron localized on Ti. Measurements with the frozen solution also point to the strong anisotropy of the g-tensor. DFT computations show that the cluster can adopt several nearly isoenergetic configurations. DFT-based Born-Oppenheimer molecular dynamics (BOMD) simulations reveal that, unlike in Sc(3)N@C(80), the cluster dynamics in TiSc(2)N@C(80) cannot be described as a 3D rotation. The cluster rotates around the Ti-N axis, while the Ti atom oscillates in one position around the pentagon/hexagon edge. Evolution of the spin populations along the BOMD trajectory has shown that the spin distribution in the cluster is very flexible, and both an intracluster and cluster-cage spin flows take place. Fourier transformation of the time dependencies of the spin populations results in the spin-flow vibrational spectra, which reveal the major spin-flow channels. It is shown that the cluster-cage spin flow is selectively coupled to one vibrational mode, thus, pointing to the utility of the clusterfullerene for the molecular spin transport. Spin-flow vibrational spectroscopy is thus shown to be a useful method for characterization of the spin dynamics in radicals with flexible spin density distribution.

Clusterfullerenes represent a novel branch of endohedral fullerenes, which are characterized by a robust fullerene cage with metal clusters encaged in its hollow. Since the discovery of nitride clusterfullerenes (NCFs) in 1999, the family of clusterfullerenes has been significantly expanded within the past decade, with new members including carbide clusterfullerenes (CCFs), hydrocarbide clusterfullerenes (HCCFs), oxide clusterfullerenes (OCFs), sulfide clusterfullerenes (SCFs), and carbonitride clusterfullerenes (CNCFs). We first present the classification of clusterfullerenes and list all the clusterfullerenes reported to date. For each type of clusterfullerenes, we review in detail their synthesis, separation, intriguing molecular structures and properties. For NCFs, as the first and most important clusterfullerenes, we point out the significance of their discovery and focus on their new synthesis and separation methods as well as the new advances. Finally the potential applications of clusterfullerenes are addressed. We conclude that clusterfullerenes appear to be the fastest growing family of endohedral fullerenes up to now, and emphasize the importance of exploring new structures and chemical functionalizations of clusterfullerenes.