Bis-Bingel-functionalization of Lu3N@Ih-C80 using a supramolecular mask to enhance the TNT-EMF reactivity

Exoedral functionalization of endohedral metallofullerenes (EMFs) is crucial to use these interesting molecules as novel materials for applications in fields such as biomedicine and organic solar cell device design. In the case of trimetallic nitride template EMFs (TNT-EMFs), many functionalization methods that work on empty fullerenes are inaccessible or less effective due to the presence of the inner cluster, which increases the electron density on the surface of the carbon cage, making them less reactive. Moreover, it has been demonstrated that the inner cluster governs the reactivity and the regioselectivity of bare TNT-EMFs. The Supramolecular Mask Strategy (SMS) has shown promising results in the functionalization of C60 and C70 and is, for the first time in this work, applied to endohedral fullerenes to obtain mono- and bis-functionalization of Lu3N@Ih-C80. The stabilization of Lu3N@Ih-C80 provided by the supramolecular host is crucial to obtaining functionalization under milder conditions and with shorter reaction times. By means of MD simulations and DFT calculations, the most favorable and stable bis-adducts have been identified, considering the alignment between the geometry imposed by the inner cluster and that permitted by the tetragonal prismatic nanocapsule host. This deposit includes parameter files of the nanocapsule and the EMFs studied (Lu3N@C80, mono- and bis-adducts) and output files of the simulations without solvent of the different systems.