DFT Studies on Intermediates for Sizeable Endohedral Metallofullerenes

“Endohedral metallofullerenes (EMFs)”, also known as metallofullerenes, are the hybrid molecules of spherical nanocarbons. The structure of EMFs consists of atomic metal(s) or metal-containing clusters enclosed inside the fullerenes. These unique EMFs have potential applications in various fields. Smalley and coworkers first reported the EMFs in 1985 [1], soon after C60 was discovered. In this chapter, we will discuss the computational studies carried out for the various types of EMFs and their potential role in industrial applications. Endohedral metallofullerenes M@C44 containing several different gap atoms of scandium and titanium family are experimentally detected. Dispersion-corrected DFT was carried out to study C44 and its fullerene derivatives to calculate the binding properties and interactions. Results showed that the computational and experimental studies agreed well with C44 and its endohedral compounds. Results predicted that C44 D2 (89) isomer is suitable for forming endohedral compounds. The binding affinity of the endohedral atom and its enclosure showed good profusion of these clusters. The DFT studies are used to study different characteristics of the doped C44-D2 (89) to the tri and tetra anions of empty C44-D2 clusters. These metal−cage bonds possess partial (ionic and covalent) interactions. The aromaticity of the cage is estimated with nucleus-independent chemical shift (NICS(0)), as it plays a vital role in balancing the endohedral species.