Endohedral metallofullerenes: An unconventional core–shell coordination union

• Endohedral metallofullerenes (EMFs) are a novel class of metal–carbon hybrid molecules.
• The structures and properties of EMFs are far more fascinating than those of other materials.
• The research on EMFs has surprisingly blossomed during recent years.
• We cover all the main aspects of EMFs in this paper.
• Our contribution is helpful to realize the future applications of EMFs.

Endohedral metallofullerenes (EMFs) are a novel class of metal–carbon hybrid molecules consisting of a fullerene shell and a metal core. Because of the presence of the internal metallic species and charge transfer from metal to cage, EMFs have unique structures and many fascinating properties, which are distinctly different from those of empty fullerenes. The research on EMFs has surprisingly blossomed during recent years, and many practical materials based on EMFs with potential applications in biomedicine, materials science and photovoltaics have been proposed. In this review, we give a systematic and comprehensive summary of the main aspects of EMFs, with emphasis given to experimental results relative to computational work. Finally, perspectives for the future development of EMFs are proposed.