Organic functionalization of endohedral metallofullerenes (EMFs) is essential to construct novel organo-metallofullerene materials for a variety of future applications. However, only a limited number of reactions with EMFs to alter the exohedral character and physical properties have been investigated to date. Notably, the TNT metallofullerenes, formed in relatively high yields, lower only than C60 and C70 in the Krätschmer-Huffman electric-arc generator, possess a closed shell electronic structure and hence are less reactive than classical EMFs. Exploring new ways to functionalize TNT metallofullerenes is crucial for expanding their potential applications.

In this presentation, we report the synthesis of novel Sc3N@C80 derivatives via photochemical reactions. Bisbenzyl adducts of Sc3N@C80 were produced in a high yield. NMR spectra revealed the high symmetry of this compound, since only one set of benzylic proton signal was detected. This synthetic method can be easily extended to other TNT metallofullerenes, such as Lu3N@C80, to generate analogues.