Stability and Electronic Properties of 1D and 2D Ca@C60 Oligomers and Polymers

Abstract

The polymerization of fullerenes is a significant method for obtaining fullerene-based materials that possess intriguing properties. Metallofullerenes, as a notable type of fullerene derivatives, are also capable of undergoing polymerization, potentially resulting in the creation of metallofullerene polymers. However, there is currently limited knowledge regarding the polymerization process of metallofullerenes. In this study, we have selected Ca@C 60 as a representative compound to investigate the polymerization process of metallofullerenes. The objective of this research is to determine whether the polymerization process is energetically favorable and to examine how the electronic properties of the metallofullerene are altered throughout the polymerization process. Ca@C 60 is a unique metallofullerene molecule that exhibits insolubility in common fullerene solvents like toluene and carbon disulfide but is soluble in aniline. This behavior suggests a potential tendency for Ca@C 60 to form oligomers and polymers that resist dissolution. However, the structures and properties of polymerized Ca@C 60 remain unknown. We employed density functional theory calculations to investigate the stability and electronic properties of one-dimensional and two-dimensional Ca@C 60 oligomers and polymers. Our findings indicate that the coalescence of Ca@C 60 monomers is energetically favorable, with a significant contribution from van der Waals interactions between the fullerene cages. The polymerization process of Ca@C 60 also involves the formation of covalent linkages, including four-atom rings and C-C single bonds. The increase in the number of the Ca@C 60 units to three and four in the oligomer leads to a significant decrease in the HOMO-LUMO gap. In the two-dimensional polymerized Ca@C 60, the organization of the monomers closely resembles the spatial configuration of carbon atoms in graphene. With a direct bandgap of 0.22 eV, the polymerized Ca@C 60 holds potential for utilization in optoelectronic devices.